As the demand for global renewable energy grows, so does the demand for more efficient energy conversion machines and better wind resource assessment. The need to convert as much energy as possible with little cost remains the biggest challenge. In the wind energy sector, the quantity of the resource “wind” is not hard to locate, as with current ground and space based remote sensing technologies, and climate reanalysis techniques, the mapping of average wind speeds across the globe is achievable. The difficulty lies in identifying the “quality” of the wind resource. “Quality” is the measure of the time variant properties of the wind, and time scale here does not represent seasonal, monthly, or the daily variability, but rather the changes within hours, minutes, seconds, and sub‐second periods. Wind possesses a highly unpredictable, and non‐universal character, which is referred to as turbulence. These intermittencies in the wind speed create variable mechanical loads on the structure of wind turbines leading to fatigue, and ultimately failure. Identifying site specific qualities of the wind resource is very crucial in the design and selection process of the wind turbine. Physical theories explaining wind turbulence phenomena over flat terrain have been critiqued and tested by observations, and in general, have achieved reasonable success in explaining surface layer wind dynamics that can be applied universally. This universality, and the extrapolation of flat terrain theories to complex terrain applications, breaks down most of the time due to the newly recognized spatial and temporal spectrum of interaction modes, mechanically and thermodynamically, with the surrounding complex terrain. In terrain as found in New Zealand, most of the wind farm development is carried out over complex terrain, with ridge top and mountainous installations. In this study, an experimental campaign was carried out over a coastal ridge top, proposed for wind farming, to investigate mean and turbulent wind flow features significant for wind turbine selection and placement across the ridge. The steep sloped faces of the ridge, high wind speeds and its proximity to the sea made this location ideal for a benchmark investigation site. Ultra‐sonic ii anemometers, a sodar (sound detection and ranging) wind profiler, and high resolution LES (large eddy simulation) numerical modelling were all utilized separately and in an interconnected way to provide a comprehensive analysis of the wind dynamics over the ridge top. The three principal components of the investigation were: the effect of the upstream topography and the thermal circulation associated with the proximity to the sea on the observed and modelled wind shear vertical profile; the role that the near upwind terrain plays in shaping the turbulence energy spectrum and influencing the predicted spectrum, ultimately affecting isotropy in the flow field and turbulence length scales; turbulence advection from far topography, and the role that far upwind terrain plays in altering the wind turbulence in a measurement area or at a single point. Results showed that the thermal wind circulations and upstream steep topography could dictate the wind shear profile, and consequently have a large impact on wind turbine height selection and placement. The sodar proved to be a very useful tool in identifying vertical shear zones associated with effects of steep upstream terrain, vertical mixing of horizontal momentum, and thermal circulation from the local sea breeze. In complex terrain, the added multi‐directional perturbations from the underlying roughness redistribute the statistical variations (measured by variances) in the three spatial dimensions. Isotropy, based on measured variances, was attained for both sites on the ridge. Isotropy also held true for the energy spectrum via Fourier analysis of the high temporal resolution data, but not for both sites. In general, local isotropy can be attained in cases of higher wind speeds and increased terrain relief. Measured spectral ratios did not converge to the limit suggested by the local isotropy hypothesis. These results identify contradictions in assessing the turbulence isotropy in both real space (statistically through variances) and Fourier space (through power spectrum analysis), which suggests caution in deriving or interpreting turbulence information for wind turbine design and selection. iii 2D‐LES experiments showed that turbulent kinetic energy (TKE) can attain long range memory of underlying terrain, which can then react accordingly with upcoming terrain. Under the high wind speed scenarios, which are suitable for wind farming, and over relatively complex terrain, the flow retained some aspects of terrain information at least 30H (H is the terrain height) upstream and downstream of the terrain. In general, as the turbulence field travels over new terrain it tends to increase in intensity downstream of that feature. The newly modified TKE field acquires geometric features from the underlying terrain; mainly these features register as amplifications in the wave structure of the field at wavelengths comparable to the height of the underlying terrain. The 2D‐LES sensitivity experiments identified key areas of high mean wind speed and turbulence in relation to terrain effects, all of which should be taken into consideration when thinking of locating a wind farm in such areas.

Traditionally, agricultural nitrous oxide (N₂O) emission of New Zealand has been measured using chambers or lysimeters, and micrometeorological flux measurement experiments have been very few. Since micrometerological flux measurement systems have the advantage of measuring spatially integrated flux values for longer time periods compared to measurements made using chambers, development and verification of such a system was needed for New Zealand's agro-meteorological conditions. In this study, efficacy of such a combined flux gradient (FG) - eddy covariance (EC) micrometeorological flux measurement system is verified by continuously measuring N₂O fluxes from some control and mitigated agricultural plots of New Zealand. The control fields had natural N₂O emission, whereas, the mitigated plots were treated with chemicals to reduce N₂O emission. In this combined FG-EC method, the turbulent eddy diffusivities were estimated using the Monin-Obukhov (M-O) similarity theory based parameterization (where diffusion velocity `dhp' was used) and a thermal approach (where eddy diffusivity `kht' was used) from the EC measurements. These transfer coefficients (kht and dhp) along with the measured N₂O concentration differences were then fitted to the traditional FG equation to compute final flux values. As the primary objective of this study, measured fluxes from two different seasons and from two approaches were compared for consistency and then verified against published results. Under this wider objective of verification of the FG-EC micrometeorological method of N₂O flux estimation, this research thesis addresses three key issues: (i) assessment of error propagation in the measured flux through the eddy diffusivity - to understand the random error dynamics of the system and to estimate precision of the overall method, (ii) quantification and separation of N₂O source area emission rates from adjacent plots - to identify the contribution of an individual plot to the measured flux when multi-plot fluxes were measured from sources with different biogenic characters, and (iii) quantification of the effect of animal grazing and mitigation on the measured flux and actual emission rate of N₂O - to assess robustness of the FG-EC micrometeorological system. As a fourth objective of this study, (iv) new scaling properties of a turbulence surface layer model of a convective atmosphere is investigated as an alternative to the standard M-O similarity theory, as significant questioning of the M-O theory has been reported in some recent publications. Results from the verification experiment showed that the daily measured flux values obtained from this combined micrometeorlogical system for control plots varied between 0-191.9 and 0-491.8 gN₂O-N.ha⁻¹.day⁻¹ for autumn and spring experiments, respectively, for the parameterization method. Similarly, the daily mean flux values were found to be 10.9 ± 0.98 and 11.7 ± 0.57 gN₂O-N.ha⁻¹.day⁻¹ for the autumn and spring seasons, respectively. All these values were found to be of the same order of previously reported values in the literature and found to verifying that this FG-EC system works well under a range of meteorological conditions within a defined error range. Therefore, when the propagated random error was computed in the final flux value using kht and dhp, the mean relative error in kht was found to be higher than the mean relative error in dhp, irrespective of stability. From a Monte-Carlo type simulation of the random error, it was found that the maximum error can be up to 80% for kht irrespective of stability, and 49% and 35% for dhp respectively for stable (1/L ≥ 0, where L is Obukhov length) and unstable (1/L < 0) atmosphere. Errors in the concentration differences were estimated based on the minimum resolvable estimates from the gas analyzer and the associated random errors were found to be 6% and 8% for unstable and stable conditions. Finally, the total mean random error in the N2Oflux values was found to be approximately of the order of 9% and 12% for the parameterization method for unstable and stable conditions, respectively, and 16.5% for the thermal method, irrespective of stability. Objective (ii) of this research was addressed by developing a `footprint fraction' based inverse footprint method. Results of the footprint analysis method were assessed, first, by comparing footprint fractions obtained from both an analytical footprint model and a `forward' simulation of a backward Lagrangian stochastic (bLs) model; and second, by comparing the source area emission rates of a control plot obtained from the footprint analysis method and from the `backward' simulation of the bLs model. It was observed that the analytical footprint fractions were realistic as they compared well with the values obtain from the bLs model. The actual emission rates were found to be on average 2.1% higher than the measured flux values for the control plots. On average 4.3% of the measured fluxes were found to be contributed by source areas outside of the field domain. Again, the proposed footprint method of emission rate estimation was found to work well under a wider range of atmospheric stability, as the inverse footprint model and bLs model based emission rates were found to correlate well (0.70 and 0.61 for autumn and spring, respectively) with a 99% statistical significance. Similarly when the effect of grazing on the N₂O fluxes was considered, a 90% enhancement in the flux values was observed after grazing, followed by a decreasing trend in fluxes. However, contrary to existing knowledge of mitigation of N₂O flux by an inhibitor, this study found no statistically significant effect of mitigation in the pastoral emission of N₂O. Error accumulation, lesser soil N₂O production potential and/or inefficiency of the FG-EC method was conjectured to be reason/s for such discrepancy and some alternative convective boundary layer turbulence scaling was tested. Separate field measurement data, including the vertical profile measurements of the convective boundary layer and sonic anemometer measurements within the surface layer were used for this purpose. The spectral analysis of the vertical wind component, temperature and heat flux revealed that this new model of the convective boundary layer, which explains atmospheric boundary layer turbulence in terms of some nonlocal parameters, is more suitable than the traditional Monin-Obukhov similarity theory based model of atmospheric turbulence where the atmospheric flow properties are local. Therefore, it can be concluded that this new model of turbulence might provide the framework for a newer model of flux estimation in future. Overall, the FG-EC model of N₂O flux estimation method seems to work well within a certain error range. However, more field applications of this FG-EC method are needed for different agro-meteorological conditions of New Zealand before this method is accepted as a standard method of flux estimation, particularly, inefficiency in detecting the effect of mitigation should be tested. Development of an alternative flux gradient model which includes nonlocal atmospheric surface parameters might also be considered as a future research objective.

The electric vehicle itself today outlives its battery, necessitating battery replacement. Lithium titanium oxide (LTO) has, in this context, been suggested as a new anode material in heavy electric vehicle applications due to intrinsic properties regarding safety, lifetime and availability. The work presented here is focused on the LTO electrode/electrolyte interface. Photoelectron spectroscopy (PES) has been applied to determine how and if the usage of LTO could prevent extensive anode-side electrolyte decomposition and build-up of a surface layer. The presence of a solid electrolyte interphase (SEI) comprising LiF, carbonates and ether compounds was found in half-cells utilizing a standard ethylene:diethylcarbonate electrolyte with 1 M LiPF6. Via testing of symmetrical LTO-LTO cells, the stability of the formed SEI was put in to question. Moreover, the traditional polyvinylidene difluoride (PVdF) binder was replaced by more environmentally benign carboxylmethyl cellulose (CMC) and polyacrilic acid (PAA) binders in LTO electrodes, and it was found that CMC helped to form a more stable surface-layer that proved beneficial for long term cycling. Following the half-cell studies, full-cells were investigated to observe how different cathodes influence the SEI of LTO. The SEI in full-cells displayed characteristics similar to the half-cells, however, when utilizing a high voltage LiNi0.5Mn1.5O4 cathode, more electrolyte decomposition could be observed. Increasing the operational temperature of this battery cell generated even more degradation products on the LTO electrodes. Mn was also found on the anode when using Mn-based cathodes, however, it was found in its ionic state and did not significantly affect the composition or behavior of the observed SEI layer. Furthermore, by exchanging the electrolyte solvent for propylene carbonate, the thickness of the SEI increased, and by replacing the LiPF6 salt for LiBF4 the stability of the SEI improved. Thus is it demonstrated that such a passivation can be beneficial for the long-term surface stability of the electrode. These findings can therefore help prolong the lifetime of LTO-based battery chemistries.

No description available.

No description available.

No description available.

<p>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.</p><p>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.</p><p>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.</p><p>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.</p>

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.

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.

<p>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.</p><p>Interface formation between the LiMn₂O₄cathode 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, Li_xPF_y (or Li_xBF_y, depending on the electrolyte salt used), Li_xPO_yF_z (or Li_xBO_yF_z) 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. </p><p>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.</p><p>A novel <i>in situ</i> 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.</p>