Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2003. / Härtill 4 uppsatser.

Le développement de lubrifiants à haute valeur ajoutée subissant des conditions opératoires de plus en plus draconiennes, économes en carburant et performants pendant une longue durée reste un défi considérable pour les fabricants d’huiles. Cette thèse concerne l’étude du rôle et des actions des améliorants d’indice de viscosité (ou Viscosity Index Improvers (VII)) dans les lubrifiants moteurs. Le premier objectif visé dans ce travail est la caractérisation des comportements rhéologiques et la modélisation de la viscosité en fonction de conditions réelles de température, pression et contrainte de cisaillement pour des solutions d’huile de base et de polymère sans additifs fonctionnels. Plusieurs polymères (PAMA, OCP et PISH) de masses moléculaires et conformations (peigne, linéaire et étoile) différentes sont utilisés à 1,2% en masse dans une huile de base minérale hydrocraquée. L’originalité de la thèse réside dans l’utilisation de rhéomètres non-commerciaux à haute pression (jusqu’à 800 MPa). Un deuxième défi réside dans la compréhension de la relation entre la réponse rhéologique des lubrifiants automobiles simplifiés et les mécanismes présents à l’échelle moléculaire en explorant les notions de conformation, de solubilité et de rayon hydrodynamique grâce à l’extension de la loi d’Einstein à haute pression. Enfin, l’étude se concentre sur le lien entre rhéologie et tribologie et par extension, entre la composition chimique du lubrifiant et la tribologie. Les épaisseurs de film sont mesurées et comparées avec les prédictions analytiques de Hamrock-Dowson et avec les simulations numériques basées sur l’équation de Reynolds généralisée en incluant les modèles rhéologiques. Les données expérimentales et numériques sont en adéquation. / The development of high value-added lubricants overcoming more and more drastic operating conditions, fuel-efficient and providing excellent performance during a long time remains a huge challenge for oil makers. This thesis is dedicated to the study of the role and the actions of Viscosity Index Improvers (VII) in engine lubricants. The first objective targeted in this work is the characterization of the rheological behaviors and the modeling of viscosity in function of realistic conditions of temperature, pressure and shear stress for polymer-thickened base oil solutions without functional additives. Several polymers (PAMA, OCP and PISH) with different molecular weights and conformations (comb, linear and star) are used with a concentration of 1.2% (w/w) in a hydrocracked mineral base oil. The originality of the thesis lies in the use of non-commercial rheometers under high pressure (up to 800 MPa). A second challenge is the understanding of the relationship between the rheological response of simplified engine lubricants and the mechanisms occurring at the molecular scale by exploring the notions of conformation, solubility and hydrodynamic radius by the extension of the Einstein’s law at high pressure. Finally, the study focuses on the link between rheology and tribology and by extrapolation, between the chemical composition of the lubricant and tribology. The film thickness is measured and compared with the Hamrock-Dowson analytical predictions and with the numerical simulations based on the generalized Reynolds’ equation including the rheological models. Both experimental and numerical data are in good agreement.

The diploma thesis deals with the study of perovskite solar cells with a regular n-i-p architecture. The theoretical part of this work is mainly focused on the stability of perovskite solar cells, i.e. thermal stability and the influence of UV radiation on final perovskite solar cell stability. Furthermore, the deposition methods, the architecture of solar cells and the materials used for the preparation of electron and hole transport layers were described in more detail. The experimental part deals with the optimization of the preparation of perovskite solar cells (especially in terms of resulting photovoltaic conversion efficiency), with a description of the structure preparation process of the final photovoltaic cell and the interpretation of the measured results.

Energy-nutrient conversion ratios, as a measure of relative agricultural efficiency for Mexico, India, in the United States, and Japan between 1951 and 1974, were calculated for protein, B-vitamins, calcium, iron and food energy production. Estimates from the different nutrient ratios showed a range in percent change of production efficiency over the twenty-four year period. Indian estimates were the most consistent with only a 7 percent variability. Japan (23 percent), United States (42 percent), and Mexico (43 percent) each showed greater variability in their efficiency estimate ranges from aggregate energy-nutrient conversion ratios. Japan was the only country for which negative trends in efficiency were observed, as estimated from calcium and iron data. There did not appear to be any pattern in the relationship of one estimate to another in the countries studied. The variability of different nutrient efficiencies suggested that conventional methods of efficiency estimation based on a conversion ratio for a single nutrient may be inappropriate. There were significant differences in mean production efficiency estimates between countries but there was no uniformity among the determinations from different nutrients. The relative rank of efficiency for the countries changed for each of the efficiency estimates, except B-vitamins, over the time period studied. Diminishing returns in energy efficiency occurred as useful energy inputs increased. In addition, individual crops displayed tendencies toward diminishing returns. Plant foods were shown to be more efficient than animal sources of food. Efficiency increases appear to be related to increased use of effective energy inputs such as fertilizers.

Philosophiae Doctor - PhD (Chemistry) / Renewable energy has become the centrepiece of research in resolving the energy crisis. One of the forms of renewable energy is solar energy. This form of energy is costly to develop. Organic molecules are promising materials for the construction of next generation photovoltaic cells considering their advantage of lower cost compared to crystalline silicon that is currently used in solar cells. This forms the basis of this research, which focused on the synthesis and characterisation of poly(3- hexylthiophene) P3HT, stannum (Sn) nanoparticles and stannum-based bimetallic stannum-titanium (SnTi), stannum-chromium (SnCr) and stannum-vanadium (SnV) nanoparticles for the application in the construction of heterojunction photovoltaic cells (PVCs).

As renewable energy production becomes more prevalent, the challenge of producing renewable dispatchable fuel for the transportation sector remains unresolved. One promising approach is to produce hydrogen from solar energy with a two step thermochemical cycle which utilizes an oxygen storage material (OSM) to split water through two reversible reactions. Due to the strong coupling between reactor design, operational parameters, and OSM properties, the direct comparison of two OSMs is not straightforward. In order to guide the designs of OSMs for two-step thermochemical hydrogen production, a methodology is developed to model the max performance possible for a two-step thermochemical cycle. The novel contribution of this model considers the strong coupling between reactor operation, OSM properties, and reactor performance. Next, a method for screening and evaluating new OSMs which utilizes thermogravimetric analysis (TGA) is proposed. With this data, the modeling method previously developed is applied to determine maximum reactor efficiency possible with new materials. This allows many materials to be evaluated quickly, and facilitates further characterization new OSMs. Additionally, by comparing the predicted maximum efficiency of a new material with the efficiency of current ones, this method facilitates the comparison of two different OSMs on equal footing.

The rapid development in perovskite solar cells (PSC) has generated a tremendous interest in the photovoltaic community. The power conversion efficiency (PCE) of these devices has increased from 3.8% in 2009 to a recent certified efficiency of over 20% which is mainly the product of the remarkable properties of the perovskite absorber material. One of the most important advances occurred with the replacement of the liquid electrolyte with a solid state hole conductor which enhanced PCE values and improved the device stability. Spiro-OMeTAD (2,2',7,7'-tetrakis(N,N'-di-p-methoxyphenylamine)- 9,9'-spirobifluorene) is the most common hole transport material in perovskite solar cells. Nevertheless, the poor conductivity, low charge transport and expensive synthetic procedure and purification have limited its commercialisation. Triphenylamines (TPA) like Spiro-OMeTAD are commonly employed due to the easy oxidation of the nitrogen centre and good charge transport. Other triarylamines have similar properties to Spiro-OMeTAD but are easier to synthesise. The aim of this doctoral thesis is to investigate different types of hole transport materials in perovskite solar cells. Three different series of triphenylamine-based HTM were designed, synthesised, characterised and studied their function in perovskite solar cells. A series of five diacetylide-triphenylamine (DATPA) derivatives (Chapter 3) with different alkyl chain length in the para position was successfully synthesised through a five step synthesis procedure. A range of characterisation techniques was carried out on the molecules including; optical, electrochemical, thermal and computational methods. The results show that the new HTMs have desirable optical and electrochemical properties, with absorption in the UV, a reversible redox property and a suitable highest occupied molecular orbital (HOMO) energy level for hole transport. Perovskite solar cell device performances were studied and discussed in detail. This project studied the effect of varying the alkyl chain length on structurally similar triarylamine-based hole transport materials on their thermal, optical, electrochemical and charge transport properties as well as their molecular packing and solar cell parameters, thus providing insightful information on the design of hole transport materials in the future. The methoxy derivative showed the best semiconductive properties with the highest charge mobility, better interfacial charge transfer properties and highest PCE value (5.63%). The use of p-type semiconducting polymers are advantageous over small molecules because of their simple deposition, low cost and reproducibility. Styrenic triarylamines (Chapter 4) were prepared by the Hartwig-Buchwald coupling followed by their radical polymerization. All monomers and polymers were fully characterised through electrochemical, spectroscopic and computational techniques showing suitable HOMO energy levels and desirable optoelectrochemical properties. The properties and performance of these monomers and polymers as HTMs in perovskite solar cells were compared in terms of their structure. Despite the lower efficiencies, the polymers showed superior reproducibility on each of the device parameters in comparison with the monomers and spiro-OMeTAD. Finally, star-shaped structures combine the advantages of both small molecules, like well-defined structures and physical properties, and polymers such as good thermal stability. Two star-shaped triarylamine-based molecules (Chapter 5) were synthesised, fully characterised and their function as hole-transport materials in perovskite solar cells studied. These materials afford a PCE of 13.63% and high reproducibility and device stability. In total this work provided three series of triarylamine-based hole transport materials for perovskite solar cells application and enabled a comparison of the pros and cons of different design structures: small-molecule, polymeric and star-shaped.

The climate affects animal populations through several processes. These processes includereproduction, phenology and the success of hunting. By influencing the phenology of species theclimate also affects the way species interact. If a climate-induced phenology change promotes abasal species to bud earlier in the spring for example, this will affect the links to other species inthe food web due to a time lag in the tropic levels above. This dependence, that a predator has tobeing synchronous to its prey, is called the match/mismatch hypothesis (MMH). Studies haveindicated that species higher up in the food web adapt slower than species lower in the food webwith shorter generation times (which creates a temporal mismatch).A climate-induced phenology change in basal species could therefore be expected to affect thedensities and extinction rates of species higher up in the food web.In this study a declining conversion efficiency for predators was used to model the effects ofclimate change on triangular food webs with three trophic levels. This was done by using ageneralized Lotka-Volterra model. The results indicate that, in a food web with three trophiclevels, the densities of herbivores and carnivores drops in response to an increased change ofclimate. The extinction rates of carnivores also increase rapidly in response to an increasedclimate change. / Klimatet påverkar djurpopulationer genom ett flertal processer. Dessa processer inkluderarreproduktion, fenologi och jaktframgång. Genom att påverka arters fenologi påverkar klimatet ävenhur arter interagerar med varandra. Om en klimatinducerad fenologiförändring stimulerar en basalart att knoppa tidigare på våren kommer det att påverka länkar till andra arter i näringsväven pågrund av en tidsförskjutning till andra trofinivåer. Detta beroende för ett rovdjur att varasynkroniserad med sitt byte kallas för match/mismatch-hypotesen (MMH). Studier har indikerat attarter högre upp i näringsväven anpassar sig långsammare än arter lägre ned i näringsväven medkortare generationstid. En klimatinducerad fenologiförändring i basala arter kan därför förväntaspåverka densiteten och utdöendehastigheten för arter högre upp i näringsväven. Studien använderen avtagande rekryteringsförmåga för att modellera klimatförändringars effekt på trianguläranäringsvävar med tre trofinivåer. För att göra detta har en generell Lotka-Volterra modell används.Från resultaten av den här studien dras också slutsatsen att, i en näringsväv med tre trofinivåer,densiteten av herbivorer och karnivorer avtar som svar på en ökad klimatförändring.Utdöendehastigheten för rovdjur ökar också snabbt som svar på en ökande klimatförändring.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv. / Härtill 5 uppsatser.

Resumo: Na região do Cerrado, a integração lavoura-pecuária sob sistema plantio direto é uma das alternativas para elevar a produtividade e o desempenho econômico de sistemas agrícolas. O trabalho de pesquisa objetivou: 1) avaliar a produtividade de grãos da cultura de milho em épocas de consorciação com o Panicum maximum cv. Tanzânia, Panicum maximum cv. Mombaça, Brachiaria brizantha cv. Marandu e Brachiaria ruziziensis; 2) avaliar a adubação nitrogenada dos capins após a colheita do milho em quatro épocas de corte no inverno/primavera quanto à produtividade de massa seca, a composição bromatológica, o índice ICF, a eficiência de conversão do N-fertilizante em forragem e a decomposição da palha após a última época de corte; 3) avaliar o efeito residual da adubação nitrogenada nos capins na cultura do milho em sucessão; 4) avaliar o desempenho econômico do milho consorciado, da pastagem adubada com nitrogênio, do milho em sucessão e do sistema como um todo, considerando o ganho de peso vivo médio diário de 0,2 e 0,6 kg/animal. Para atingir tais propósitos, foram conduzidos três experimentos sequenciais, durante os anos agrícolas de 2007/08 e 2008/09 na Fazenda de Ensino, Pesquisa e Extensão, da Faculdade de Engenharia - Unesp, Campus de Ilha Solteira, em um Latossolo Vermelho distroférrico em condições de cerrado, com histórico de cinco anos sob sistema plantio direto. O delineamento experimental utilizado foi o de blocos casualizados, com quatro repetições. No experimento I (2007/2008), os tratamentos foram constituídos de oito consórcios da cultura do milho com capins (semeado simultaneamente ou por ocasião da adubação nitrogenada de cobertura) e do milho sem consorciação. No expetimento II, após a colheita da cultura do milho (2007/2008), em esquema de parcelas subdivididas constituídas pela ausência e doses de 200, 400 e 800 kg/ha/ano de N na ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In the Brazilian "Cerrado" conditions, the crop-livestock integration under no-tillage system is an alternative to increase the yield and the economic performance of agricultural systems. The present work aimed: 1) to evaluate corn grain yield under different intercropping times with Panicum maximum cv. Tanzânia, Panicum maximum cv. Mombaça, Brachiaria brizantha cv. Marandu e Brachiaria ruziziensis; 2) to evaluate the nitrogen fertilization of the grasses after the corn harvest in four seasons cut in the winter/spring, considering the dry mass yield, chemical composition, ICF index, conversion efficiency of N-fertilizer on forage and the straw decomposition in "Litter-bags" after the last season of cut; 3) to evaluate the residual effect of nitrogen fertilization on grasses in corn crop in succession; 4) to evaluate to economic performance of corn intercropped, pasture fertilized with nitrogen, the corn crop in succession and the crop-livestock integration system as a whole, considering the daily weight gain of 0.2 and 0.6 kg/animal. To reach these purposes, they were conducted three sequenced studies during the 2007/2008 and 2008/2009 growing seasons, at Experimental Station from College of Engineering in Ilha Solteira, São Paulo State, Brazil, in a Red Latosol (Oxisol) in "Cerrado" conditions, with a history of five years under no-tillage system. The experimental design was a completely randomized block, with four replicates. In the experiment I (2007/2008), the treatments consisted of eigth methods for growing corn intercropped with Panicum maximum cv. Tanzania, Panicum maximum cv. Mombaça, Brachiaria brizantha cv. Marandu, and Brachiaria ruziziensis, sown simultaneously or at time of side dressing nitrogen fertilization, besides single grown corn. In the experiment II, after the corn harvest (2007/2008), in split-plot scheme was applied urea at side dressing ... (Complete abstract click electronic access below) / Orientador: Marcelo Andreotti / Coorientador: Antonio Fernando Bergamaschine / Banca: Enes Furlani Júnior / Banca: Ciniro Costa / Mestre