LiMn2O4 is ideal as a high-capacity Li-ion battery cathode material by virtue of its low toxicity, low cost, and the high natural abundance of Mn. Surface related reactions and bulk kinetics have been the major focus of this work. The main techniques exploited have been: electrochemical cycling, X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy and thermal analysis. Interface formation between the LiMn2O4 cathode and carbonate-based electrolytes has been followed under different pre-treatment conditions. The variables have been: number of charge/discharge cycles, storage time, potential, electrolyte salt and temperature. The formation of the surface layer was found not to be governed by electrochemical cycling. The species precipitating on the surface of the cathodes at ambient temperature have been determined to comprise a mixture of organic and inorganic compounds: LiF, LixPFy (or LixBFy, depending on the electrolyte salt used), LixPOyFz (or LixBOyFz) and poly(oxyethylene). Additional compounds were found at elevated temperatures: phosphorous oxides (or boron oxides) and polycarbonates. A model has been presented for the formation of these surface species at elevated temperatures. The cathode surface structure was found to change towards a lithium-rich and Mn3+-rich compound under self-discharge. The reduction of LiMn2O4, in addition to the high operating potential, induces oxidation of the electrolyte at the cathode surface. A novel in situ electrochemical/structural set-up has facilitated a study of the kinetics in the LiMn2O4 electrode. The results eliminate solid-phase diffusion as the rate-limiting factor in electrochemical cycling. The electrode preparation method used results in good utilisation of the electrode, even at high discharge rates.

Polythermal glaciers, i.e. glaciers with a combination of ice at and below the freezing point, are widespread in arctic and subarctic environments. The polythermal structure has major implications for glacier hydrology, ice flow and glacial erosion. However, the interplay of factors governing its spatial and temporal variations such as net mass balance, ice advection and water content in the ice is poorly investigated and as yet not fully understood. This study deals with a thorough investigation of the polythermal regime on Storglaciären, northern Sweden, a small valley glacier with a cold surface layer in the ablation area. Extensive field work was performed including mapping of the cold surface layer using ground-penetrating radar, ice temperature measurements, mass balance and ice velocity measurements. Analyses of these data combined with numerical modelling were used specifically to investigate the spatial and temporal variability of the cold surface layer, the spatial distribution of the water content just below the cold surface layer transition, the effect of radar frequency on the detection of the surface layer, and the sensitivity of the cold surface layer to changes in forcing. A comparison between direct temperature measurements in boreholes and ground-penetrating surveys shows that the radar-inferred cold-temperate transition depth is within ±1 m from the melting point of ice at frequencies above ~300 MHz. At frequencies below ~155 MHz, the accuracy degrades because of reduced scattering efficiency that occurs when the scatterers become much smaller compared to the wavelength. The mapped spatial pattern of the englacial cold-temperate transition boundary is complex. This pattern reflects the observed spatial variation in net loss of ice at the surface by ablation and vertical advection of ice, which is suggested to provide the predominant forcing of the cold surface layer thickness pattern. This is further supported by thermomechanical modeling of the cold surface layer, which indicates high sensitivity of the cold surface layer thickness to changes in vertical advection rates. The water content is the least investigated quantity that is relevant for the thermal regime of glaciers, but also the most difficult to assess. Spatial variability of absolute water content in the temperate ice immediately below the cold surface layer on Storglaciären was determined by combining relative estimates of water content from ground-penetrating radar data with absolute determination from temperature measurements and the thermal boundary condition at the freezing front. These measurements indicate large-scale spatial variability in the water content, which seems to arise from variations in entrapment of water at the firn-ice transition. However, this variability cannot alone explain the spatial pattern in the thermal regime on Storglaciären. Repeated surveys of the cold surface layer show a 22% average thinning of the cold surface layer on Storglaciären between 1989 and 2001. Transient thermomechanical modeling results suggest that the cold surface layer adapts to new equilibrium conditions in only a few decades after a perturbation in the forcing is introduced. An increased winter air temperature since mid-1980s seems to be the cause of the observed thinning of the cold surface layer. Over the last decades, mass balance measurements indicate that the glacier has been close to a steady state. The quasi-steady state situation is also reflected in the vertical advection, which shows no significant changes during the last decades. Increased winter temperatures at the ice surface would result in a slow-down of the formation of cold ice at the base of the cold surface layer and lead to a larger imbalance between net loss of ice at the surface and freezing of temperate ice at the cold-temperate transition.

O desgaste superficial por abrasão é uma manifestação patológica que decorre do atrito entre partículas secas e a superfície do material, causando uma perda progressiva das camadas mais externas da estrutura. Entender esse mecanismo de deterioração e ainda os parâmetros que influenciam a sua ocorrência são preocupações válidas, visto que ele compromete a durabilidade e a funcionalidade de estruturas, tais como pisos de concreto. Além disso, a correção desta manifestação patológica exige gastos elevados com reparo ou substituição do concreto e, dessa maneira, a necessidade de maiores estudos buscando ações mais efetivas na prática é justificada. Neste particular, estudou-se a influência das propriedades relacionadas à matriz e à superfície na resistência à abrasão dos compósitos. Para tanto, alguns fatores que influenciam na qualidade dos concretos empregados em pisos, como o tipo de cimento (CP IV; CP V-ARI), a relação água/aglomerante (0,40; 0,60), o teor de substituição de sílica ativa (0%; 10%) e o tipo de cura (submersa; caixa aquecida) foram avaliados. Os ensaios adotados para estudar a influência das propriedades de massa no mecanismo de degaste foram os de resistência à compressão uniaxial, resistência à tração na flexão e exsudação. Já os ensaios para verificar a influência das propriedades de superfície na magnitude desse mecanismo foram os de dureza superficial, resistência à abrasão, porosimetria por intrusão de mercúrio, microdureza por indentação, análises em microscópio estereoscópico e a digitalização tridimensional à laser. Os resultados encontrados mostraram uma influência estatística significativa do tipo de cimento sobre todas as propriedades avaliadas, sendo que o cimento de alta resistência inicial apresentou melhor desempenho em comparação ao cimento pozolânico, considerando uma mesma idade de análise (63 dias). Além disso, verificou-se uma influência estatística significativa da relação a/agl no comportamento dos concretos, onde a relação a/agl 0,6 aumentou os índices de desgaste das amostras em relação as de referência (a/agl 0,4), conforme esperado. Quanto ao tipo de cura, os compósitos curados de forma submersa apresentaram os melhores resultados frente ao desgaste superficial comparando-se àqueles mantidos na cura em caixa aquecida. Finalmente, analisando o teor de substituição de sílica ativa, observou-se que a substituição de 10 % sobre a massa de cimento proporcionou acréscimos estatisticamente significativos na resistência à abrasão das amostras com menor relação a/agl; somando-se a isto, a presença da sílica minimizou o efeito da cura em caixa aquecida na camada superficial das amostras de concreto submetidas ao desgaste. Concluindo, a resistência à abrasão dos concretos mostrou ter uma importante relação não somente com as suas propriedades de massa, mas também com a qualidade da sua camada superficial, uma vez que apresentou forte correlação com as características de superfície avaliadas, como a dureza superficial, a microdureza e a porosimetria ao mercúrio. Além disso, salienta-se que o ensaio de dureza superficial por esclerometria poderia ser adotado como parâmetro para determinação direta da resistência ao desgaste e sugere-se que a exsudação dos pisos de concreto venha a ser o fator principal no controle da qualidade da camada superficial da placa de concreto. / Surface abrasion wear is a pathological manifestation triggered by friction between dried particles and the surface of the material, provoking a progressive loss of the outermost layers. The comprehension of this mechanism of deterioration and also the parameters that influence its occurrence are valid concerns, since it compromises the durability and functionality of structures such as concrete floors. In addition, repair this pathological manifestation or replace the damage concrete require high expenditure. Thus, the necessity of further studies seeking for practical effective actions is justified. In this particular, the aim of this work was to study the influence of properties related to the matrix and the surface of composites on abrasion resistance. For this purpose, some factors that influence the quality of the concrete used in floors, including the cement type (CP IV; CP V-ARI), the water / binder ratio (0.40, 0.60), the replacement content of silica fume (0%, 10%) and the conditions of cure (submerged; heat box) were evaluated. The assays employed in order to study the influence of mass properties on the wear mechanism were the compressive strength, flexural tensile strength and bleeding. As regards to the influence of surface properties on the magnitude of this mechanism, it was verified by testing the surface hardness, abrasion resistance, porosimetry by mercury intrusion, microhardness by indentation, analysis in stereoscopic microscope and three-dimensional laser scanning. The obtained data demonstrated a statistically significant influence of cement type on all assessed properties, with the high early strength cement presenting a better performance as compared to pozzolan cement, considering a similar age of analysis (63 days). Furthermore, there was a statistically significant influence of water / binder ratio on concrete behavior, where the water / binder ratio of 0.6 increased the wear rates of the samples in comparison to the reference (water / binder 0.4), as expected. Regarding to the conditions of cure, the submerged composites showed better results against surface wear as compared to those kept in the heat box. Finally, it was observed that the replacement content of silica fume of 10% on the cement mass provided statistically significant increases in abrasion resistance of samples with lower water / binder ratio. In addition, the presence of silica minimized the effects of curing in a heat box on the surface layer of concrete samples that were submitted to wear. In conclusion, the abrasion resistance of concretes demonstrated an important relationship not only with the mass properties of these structures but also with the quality of their surface layer, since a strong correlation with the evaluated surface features was observed, including surface hardness, microhardness and porosimetry by mercury intrusion. Moreover, it is emphasized that the surface hardness assay by rebound hammer may be used as a parameter for direct determination of wear resistance and it is suggested that bleeding of concrete floors might be the main factor for controlling the surface layer quality of the concrete slab.

O desgaste superficial por abrasão é uma manifestação patológica que decorre do atrito entre partículas secas e a superfície do material, causando uma perda progressiva das camadas mais externas da estrutura. Entender esse mecanismo de deterioração e ainda os parâmetros que influenciam a sua ocorrência são preocupações válidas, visto que ele compromete a durabilidade e a funcionalidade de estruturas, tais como pisos de concreto. Além disso, a correção desta manifestação patológica exige gastos elevados com reparo ou substituição do concreto e, dessa maneira, a necessidade de maiores estudos buscando ações mais efetivas na prática é justificada. Neste particular, estudou-se a influência das propriedades relacionadas à matriz e à superfície na resistência à abrasão dos compósitos. Para tanto, alguns fatores que influenciam na qualidade dos concretos empregados em pisos, como o tipo de cimento (CP IV; CP V-ARI), a relação água/aglomerante (0,40; 0,60), o teor de substituição de sílica ativa (0%; 10%) e o tipo de cura (submersa; caixa aquecida) foram avaliados. Os ensaios adotados para estudar a influência das propriedades de massa no mecanismo de degaste foram os de resistência à compressão uniaxial, resistência à tração na flexão e exsudação. Já os ensaios para verificar a influência das propriedades de superfície na magnitude desse mecanismo foram os de dureza superficial, resistência à abrasão, porosimetria por intrusão de mercúrio, microdureza por indentação, análises em microscópio estereoscópico e a digitalização tridimensional à laser. Os resultados encontrados mostraram uma influência estatística significativa do tipo de cimento sobre todas as propriedades avaliadas, sendo que o cimento de alta resistência inicial apresentou melhor desempenho em comparação ao cimento pozolânico, considerando uma mesma idade de análise (63 dias). Além disso, verificou-se uma influência estatística significativa da relação a/agl no comportamento dos concretos, onde a relação a/agl 0,6 aumentou os índices de desgaste das amostras em relação as de referência (a/agl 0,4), conforme esperado. Quanto ao tipo de cura, os compósitos curados de forma submersa apresentaram os melhores resultados frente ao desgaste superficial comparando-se àqueles mantidos na cura em caixa aquecida. Finalmente, analisando o teor de substituição de sílica ativa, observou-se que a substituição de 10 % sobre a massa de cimento proporcionou acréscimos estatisticamente significativos na resistência à abrasão das amostras com menor relação a/agl; somando-se a isto, a presença da sílica minimizou o efeito da cura em caixa aquecida na camada superficial das amostras de concreto submetidas ao desgaste. Concluindo, a resistência à abrasão dos concretos mostrou ter uma importante relação não somente com as suas propriedades de massa, mas também com a qualidade da sua camada superficial, uma vez que apresentou forte correlação com as características de superfície avaliadas, como a dureza superficial, a microdureza e a porosimetria ao mercúrio. Além disso, salienta-se que o ensaio de dureza superficial por esclerometria poderia ser adotado como parâmetro para determinação direta da resistência ao desgaste e sugere-se que a exsudação dos pisos de concreto venha a ser o fator principal no controle da qualidade da camada superficial da placa de concreto. / Surface abrasion wear is a pathological manifestation triggered by friction between dried particles and the surface of the material, provoking a progressive loss of the outermost layers. The comprehension of this mechanism of deterioration and also the parameters that influence its occurrence are valid concerns, since it compromises the durability and functionality of structures such as concrete floors. In addition, repair this pathological manifestation or replace the damage concrete require high expenditure. Thus, the necessity of further studies seeking for practical effective actions is justified. In this particular, the aim of this work was to study the influence of properties related to the matrix and the surface of composites on abrasion resistance. For this purpose, some factors that influence the quality of the concrete used in floors, including the cement type (CP IV; CP V-ARI), the water / binder ratio (0.40, 0.60), the replacement content of silica fume (0%, 10%) and the conditions of cure (submerged; heat box) were evaluated. The assays employed in order to study the influence of mass properties on the wear mechanism were the compressive strength, flexural tensile strength and bleeding. As regards to the influence of surface properties on the magnitude of this mechanism, it was verified by testing the surface hardness, abrasion resistance, porosimetry by mercury intrusion, microhardness by indentation, analysis in stereoscopic microscope and three-dimensional laser scanning. The obtained data demonstrated a statistically significant influence of cement type on all assessed properties, with the high early strength cement presenting a better performance as compared to pozzolan cement, considering a similar age of analysis (63 days). Furthermore, there was a statistically significant influence of water / binder ratio on concrete behavior, where the water / binder ratio of 0.6 increased the wear rates of the samples in comparison to the reference (water / binder 0.4), as expected. Regarding to the conditions of cure, the submerged composites showed better results against surface wear as compared to those kept in the heat box. Finally, it was observed that the replacement content of silica fume of 10% on the cement mass provided statistically significant increases in abrasion resistance of samples with lower water / binder ratio. In addition, the presence of silica minimized the effects of curing in a heat box on the surface layer of concrete samples that were submitted to wear. In conclusion, the abrasion resistance of concretes demonstrated an important relationship not only with the mass properties of these structures but also with the quality of their surface layer, since a strong correlation with the evaluated surface features was observed, including surface hardness, microhardness and porosimetry by mercury intrusion. Moreover, it is emphasized that the surface hardness assay by rebound hammer may be used as a parameter for direct determination of wear resistance and it is suggested that bleeding of concrete floors might be the main factor for controlling the surface layer quality of the concrete slab.

The method of acoustic tomography, based on external sonic energy, is applied inside the atmospheric surface layer to observe near-surface temperature fields. Important advantages of this technique as compared to other measurement methods are their remote-sensing capacity and the possibility to directly derivate area-averaged meteorological quantities. The needed input data for the tomographically inverse algorithm are provided by the interaction of sound waves with the scanned atmospheric layer. The resulting horizontal slices lead to statements on the inhomogeneity of the underlying surface which may result in noticeable difficulties during the analysis of measuring campaigns with conventional methods. / Die auf der Aussendung von Schallenergie basierende Methode der akustischen Tomographie wird in der atmosphärischen Bodenschicht angewendet, um bodennahe Temperaturfelder zu beobachten. Bedeutende Vorteile dieses Verfahrens im Vergleich zu anderen Meßmethoden sind die Fernerkundungskapazität und die Möglichkeit, flächengemittelte Werte meteorologischer Größen direkt abzuleiten. Die für den tomographischen Invertierungsalgorithmus benötigten Eingangsdaten werden durch die Wechselwirkung von Schallwellen mit der durchstrahlten Luftschicht bereitgestellt. Die resultierenden horizontalen Schnittbilder führen zu Darstellungen der Inhomogenität der Oberfläche. Letztere können beachtliche Schwierigkeiten während der Analyse von Messkampagnen mit konventionellen Methoden hervorrufen.

<div>Red blood cells (RBCs) make up 40-45% of blood and play an important role in oxygen transport. That transport depends on the RBC distribution throughout the body, which is highly heterogeneous. That distribution, in turn, depends on how RBCs are distributed or partitioned at diverging vessel bifurcations where one vessel flows into two. Several studies have used mathematical modeling to consider RBC partitioning at such bifurcations in order to produce useful insights. However, these studies assume that the vessel wall is a flat impenetrable homogeneous surface. While this is a good first approximation, especially for larger vessels, the vessel wall is typically coated by a flexible, porous endothelial surface layer (ESL) that is 0.5-1 microns thick. To better understand the possible effects of this layer on RBC partitioning, a diverging capillary bifurcation is analyzed using a flexible, two-dimensional RBC model. The model is also used to investigate RBC deformation and penetration of the ESL region when ESL properties are varied. The RBC is represented using interconnected viscoelastic elements. Stokes flow equations (viscous flow) model the surrounding fluid. The flow in the ESL is modeled using the Brinkman approximation for porous media with a corresponding hydraulic resistivity. The resistance of the ESL to compression is modeled using an osmotic pressure difference. The study includes isolated cells that pass through the bifurcation one at a time with no cell-cell interactions and two cells that pass through the bifurcation at the same time and interact with each other. A range of physiologically relevant hydraulic resistivities and osmotic pressure differences are explored.</div><div><br></div><div>For isolated cell simulations, decreasing hydraulic resistivity and/or decreasing osmotic pressure difference produced four behaviors: 1) RBC distribution nonuniformity increased; 2) RBC deformation decreased; 3) RBCs slowed down slightly; and 4) RBCs penetrated more deeply into the ESL. The presence of an altered flow profile and the ESL's resistance to penetration were primary factors responsible for these behaviors. In certain scenarios, ESL penetration was deep enough to present a possibility of cell adhesion, as can occur in pathological situations.</div><div><br></div><div>For paired cell simulations, more significant and complex changes were observed. Three types of effects that alter partitioning as hydraulic resistivity is changed are identified. Decreasing hydraulic resistivity in the ESL produced lower RBC deformation. Including cell-cell interactions tended to increase deformation sharply compared to isolated cell scenarios. ESL penetration generally decreased for lower hydraulic resistivities except in scenarios with significant cell-cell interactions. This was primarily due to changes in flow profiles induced by the altered hydraulic resistivity levels.</div>

No description available.

Appropriate calculation of surface turbulent fluxes between the atmosphere and the underlying surface is one of the major challenges in geosciences. In practice, the surface turbulent fluxes are estimated from the mean surface meteorological variables based on the bulk transfer model combined with Monnin-Obukhov Similarity (MOS) theory. Few studies have been done to examine the extent that to which this flux parameterization framework can be applied to different weather and surface conditions. A novel validation method is developed in this thesis research, which is applied to evaluate the surface flux parameterization using in-situ observations. The main findings are: (a) the theoretical prediction that uses MOS theory does not match well with those directly computed from the observations collected in the coastal region. (b) Large spread in exchange coefficients mainly occurs in the calm wind regime with strong stability. (c) Large turbulent eddies, which depend largely on the mean flow and surface conditions, tend to break the constant flux assumption in the surface layer.

This thesis is dealing with an analysis of thermal and mechanical loads on a work-roll. First, hot rolling focused on work-roll is described in general. A theoretical analysis of roll loads and the mechanisms affecting roll durability are presented here. The thesis is concentrated on creation of a model in FEM program ANSYS. The final model is loaded with different rolling schemes and monitored stresses in a surface layer. The parameters obtained from the measurements performed in a rolling mill are applied as boundary conditions within the model.

<p>U okviru doktorske disertacije predstavljeni su postojeći i novi koncepti modeliranja<br />turbulentnog transporta ugljen-dioksida i azotnih oksida u povr&scaron;inskom sloju atmosfere<br />iznad ruralne oblasti. Cilj istraživanja je da se na osnovu postojećih saznanja o procesima<br />koji opisuju interakciju tlo-vegetacija-atmosfera i rezultata mikrometeorolo&scaron;kih<br />eksperimenata unapredi modeliranje procesa interakcije. Poseban akcenat stavljen je na<br />modeliranje turbulentnog transporta gasova iznad i unutar &scaron;umskog sklopa. Uticaj<br />vertikalne heterogenosti biljnog sklopa uveden je u predloženi postupak skaliranja<br />asimilacije ugljen-dioksida sa lista na biljni sklop i suve depozicije azotnih oksida.<br />Predloženi koncepti testirani su u okviru fizičke LAPS i hemijske MLC-Chem povr&scaron;inske<br />sheme. Za potrebe modeliranja turbulentnog transporta ugljen-dioksida razvijen je<br />modul za parametrizaciju intenziteta fotosinteze. Kvantitativna analiza rezultata izvedena<br />je poređenjem osmotrenih i simuliranih vrednosti turbulentnih flukseva ugljen-dioksida i<br />azotnih oksida na četiri karakteristična &scaron;umska sklopa. Unapređenje modeliranja<br />izvedeno je kaplovanjem testiranih povr&scaron;inskih shema u MLC-LAPS shemu. Kvalitet<br />simulacija MLC-LAPS sheme proveren je poređenjem izlaznih i osmotrenih<br />mikrometeorolo&scaron;kih veličina, koncentracije i turbulentnih flukseva gasova.</p> / <p>This PhD thesis deals with the current and new concepts of modeling turbulent<br />transport of carbon dioxide and nitrogen oxides in the surface layer of the atmosphere<br />above the rural areas. The aim of this research is to improve modeling of the interaction<br />between soil-vegetation-atmosphere based on existing knowledge about the processes<br />describing the interaction and results of micrometeorological experiments. Special<br />emphasis is placed on the modeling of turbulent transport of gases above and within<br />the forest canopy. Influence of vertical canopy heterogeneity was introduced in the<br />proposed method for scaling the assimilation of carbon dioxide from the leaf to canopy level and dry deposition of nitrogen oxides. The presented concepts are tested within the physical LAPS and chemical MLC-Chem surface schemes. For the purposes of modeling the turbulent transport of carbon dioxide the module for parameterization of photosynthesis was developed. Quantitative analysis of the results were made by comparing the observed and simulated values of turbulent fluxes of carbon dioxide and nitrogen oxides in four distinctive forest canopies. Modeling improvement was performed by coupling tested surface schemes into MLC-LAPS scheme. Quality of MLCLAPS scheme simulations is verified by comparing the output and observed micrometeorological elements and turbulent fluxes of energy and gases.</p>