Current methods and advances in forecasting of wind power generation

Wind power generation differs from conventional thermal generation due to the stochastic nature of wind. Thus wind power forecasting plays a key role in dealing with the challenges of balancing supply and demand in any electricity system, given the uncertainty associated with the wind farm power output. Accurate wind power forecasting reduces the need for additional balancing energy and reserve power to integrate wind power. Wind power forecasting tools enable better dispatch, scheduling and unit commitment of thermal generators, hydro plant and energy storage plant and more competitive market trading as wind power ramps up and down on the grid. This paper presents an in-depth review of the current methods and advances in wind power forecasting and prediction. Firstly, numerical wind prediction methods from global to local scales, ensemble forecasting, upscaling and downscaling processes are discussed. Next the statistical and machine learning approach methods are detailed. Then the techniques used for benchmarking and uncertainty analysis of forecasts are overviewed, and the performance of various approaches over different forecast time horizons is examined. Finally, current research activities, challenges and potential future developments are appraised.

Silica bonded stationary phases: Innovative functionalization methods and novel chromatographic separations based on molecular recognition

The research work included in this thesis examines the synthesis, characterization and chromatographic evaluation of novel bonded silica stationary phases. Innovative methods of preparation of silica hydride intermediates and octadecylsilica using a “green chemistry” approach eliminate the use of toxic organic solvents and exploit the solvating power and enhanced diffusivity of supercritical carbon dioxide to produce phases with a surface coverage of bonded ligands which is comparable to, or exceeds, that achieved using traditional organic solvent-based methods. A new stationary phase is also discussed which displays chromatographic selectivity based on molecular recognition. Chapter 1 introduces the chemistry of silica stationary phases, the retention mechanisms and theories on which reversed-phase liquid chromatography and hydrophilic interaction chromatograpy are based, the art and science of achieving a well packed liquid chromatography column, the properties of supercritical carbon dioxide and molecular recognition chemistry. Chapter 2 compares the properties of silica hydride materials prepared using supercritical carbon dioxide as the reaction medium with those synthesized in an organic solvent. A higher coverage of hydride groups on the silica surface is seen when a monofunctional silane is reacted in supercritical carbon dioxide while trifunctional silanes result in a phase which exhibits different properties depending on the reaction medium used. The differing chromatographic behaviour of these silica hydride materials prepared using supercritical carbon dioxide and using organic solvent are explored in chapter 3. Chapter 4 focusses on the preparation of octadecylsilica using mono-, di- and trifunctional alkoxysilanes in supercritical carbon dioxide and in anhydrous toluene. The surface coverage of octadecyl groups, as calculated using thermogravimetric analysis and elemental analysis, is highest when a trifunctional alkoxysilane is reacted with silica in supercritical carbon dioxide. A novel silica stationary phase is discussed in chapter 5 which displays selectivity for analytes based on their hydrogen bonding capabilities. The phase is also highly selective for barbituric acid and may have a future application in the solid phase extraction of barbiturates from biological samples.

Surveillance during pregnancy: methods and response rates from a hospital based pilot study of the Pregnancy Risk Assessment Monitoring System in Ireland

Background: Many European countries including Ireland lack high quality, on-going, population based estimates of maternal behaviours and experiences during pregnancy. PRAMS is a CDC surveillance program which was established in the United States in 1987 to generate high quality, population based data to reduce infant mortality rates and improve maternal and infant health. PRAMS is the only on-going population based surveillance system of maternal behaviours and experiences that occur before, during and after pregnancy worldwide.Methods: The objective of this study was to adapt, test and evaluate a modified CDC PRAMS methodology in Ireland. The birth certificate file which is the standard approach to sampling for PRAMS in the United States was not available for the PRAMS Ireland study. Consequently, delivery record books for the period between 3 and 5 months before the study start date at a large urban obstetric hospital [8,900 births per year] were used to randomly sample 124 women. Name, address, maternal age, infant sex, gestational age at delivery, delivery method, APGAR score and birth weight were manually extracted from records. Stillbirths and early neonatal deaths were excluded using APGAR scores and hospital records. Women were sent a letter of invitation to participate including option to opt out, followed by a modified PRAMS survey, a reminder letter and a final survey.Results: The response rate for the pilot was 67%. Two per cent of women refused the survey, 7% opted out of the study and 24% did not respond. Survey items were at least 88% complete for all 82 respondents. Prevalence estimates of socially undesirable behaviours such as alcohol consumption during pregnancy were high [>50%] and comparable with international estimates.Conclusion: PRAMS is a feasible and valid method of collecting information on maternal experiences and behaviours during pregnancy in Ireland. PRAMS may offer a potential solution to data deficits in maternal health behaviour indicators in Ireland with further work. This study is important to researchers in Europe and elsewhere who may be interested in new ways of tailoring an established CDC methodology to their unique settings to resolve data deficits in maternal health.

Response to the review of the white paper on Irish aid. The urbanisation of poverty: drawing on the skills and techniques of spatial planning to support the aid programme

Submission on behalf of UCC to the Government Consultation on the White paper on Irish Aid

New phosphorescence based probes and techniques for the analysis of cellular oxygen and respiration

Real time monitoring of oxygenation and respiration is on the cutting edge of bioanalysis, including studies of cell metabolism, bioenergetics, mitochondrial function and drug toxicity. This thesis presents the development and evaluation of new luminescent probes and techniques for intracellular O2 sensing and imaging. A new oxygen consumption rate (OCR) platform based on the commercial microfluidic perfusion channel μ-slides compatible with extra- and intracellular O2 sensitive probes, different cell lines and measurement conditions was developed. The design of semi-closed channels allowed cell treatments, multiplexing with other assays and two-fold higher sensitivity to compare with microtiter plate. We compared three common OCR platforms: hermetically sealed quartz cuvettes for absolute OCRs, partially sealed with mineral oil 96-WPs for relative OCRs, and open 96-WPs for local cell oxygenation. Both 96-WP platforms were calibrated against absolute OCR platform with MEF cell line, phosphorescent O2 probe MitoXpress-Intra and time-resolved fluorescence reader. Found correlations allow tracing of cell respiration over time in a high throughput format with the possibility of cell stimulation and of changing measurement conditions. A new multimodal intracellular O2 probe, based on the phosphorescent reporter dye PtTFPP, fluorescent FRET donor and two-photon antennae PFO and cationic nanoparticles RL-100 was described. This probe, called MM2, possesses high brightness, photo- and chemical stability, low toxicity, efficient cell staining and high-resolution intracellular O2 imaging with 2D and 3D cell cultures in intensity, ratiometric and lifetime-based modalities with luminescence readers and FLIM microscopes. Extended range of O2 sensitive probes was designed and studied in order to optimize their spectral characteristics and intracellular targeting, using different NPs materials, delivery vectors, ratiometric pairs and IR dyes. The presented improvements provide useful tool for high sensitive monitoring and imaging of intracellular O2 in different measurement formats with wide range of physiological applications.

The Kyoto School and Confucianism: a Confucian reading of the philosophy of history and political thought of Masaaki Kosaka

This dissertation examines the philosophy of Masaaki Kōsaka (1900-1969) from the East Asian perspective of Confucianism, which I believe is the most appropriate moral paradigm for comprehending his political speculations. Although largely neglected in post-war scholarship, Kōsaka was a prominent member of the Kyoto School during the 1930s and 40s. This was a group of Japanese thinkers strongly associated with the philosophies of Kitarō Nishida and Hajime Tanabe. Kōsaka is now best known for his participation in the three Chūō Kōron symposia held in 1941 and 1942. These meetings have been routinely denounced by liberal historians due to the participants’ support for the Pacific War and the Co-Prosperity Sphere. However, many of these liberal portrayals have failed to take into account the full extent of the group’s resistance to the military junta of Hideki Tōjō. Adopting the methods and techniques of the empirical disciplines of academic history and Orientalism, I develop an interpretative framework that is more receptive to the political values that mattered to Kōsaka as a Confucian inspired intellectual. This has necessitated the rejection of moral history, which typically prioritises modern liberal values brought a priori to the historical record of wartime Japan, as well as recognition of the different ontological foundations that inform the unique political theories of the East Asian intellectual tradition. Reinforced by the prior research of Michel Dalissier and Graham Parkes, as well as my own reading of the Confucian canon, I adopt David Williams’s thesis of ‘Confucian Revolution’ as my principle schema of interpretation. This, I believe, is better able to reconcile Kōsaka’s support for the war with his strong condemnation of the imperialist practices of the Japanese military. Moreover, acknowledging the importance of Confucianism allows us to fully appreciate Kōsaka’s strong affinity for Kant’s practical metaphysics, Hegel’s political philosophy and Ranke’s historiography.

The role of structure in the electrochemical performance of nanostructured metal oxides for lithium ion battery anodes

The Li-ion battery has for a number of years been a key factor that has enabled an ever increasing number of modern consumer devices, while in recent years has also been sought to power a range of emerging electric and hybrid electric vehicles. Due to their importance and popularity, a number of characteristics of Li-ion batteries have been subjected to intense work aimed at radical improvement. Although electrode material selection intrinsically defines characteristics like maximum capacity or voltage, engineering of the electrode structure may yield significant improvements to the lifetime performance of the battery, which would not be available if the material was used in its bulk form. The body of work presented in this thesis describes the relationship between the structure of electrochemically active materials and the course of the electrochemical processes occurring within the electrode. Chapter one describes the motivation behind the research presented herein. Chapter two serves to highlight a number of key advancements which have been made and detailed in the literature over recent years, pertaining to the use of nanostructured materials in Li-ion technology. Chapter three details methods and techniques applied in developing the body of work presented in this thesis. Chapter four details structural, molecular and electrochemical characteristics of tin oxide nanoparticle based electrodes, with particular emphasis on the relationship between the size distribution and the electrode performance. Chapter five presents findings of structural, electrochemical and optical study of indium oxide nanoparticles grown on silicon by molecular beam epitaxy. In chapter 6, tin oxide inverted opal electrodes are investigated for the conduct of the electrochemical performance of the electrodes under varying rate of change of potential. Chapter 7 presents the overall conclusions drawn from the results presented in this thesis, coupled with an indication of potential future work which may be explored further.

Preparation and characterisation of ceria particles

Cerium dioxide (ceria) nanoparticles have been the subject of intense academic and industrial interest. Ceria has a host of applications but academic interest largely stems from their use in the modern automotive catalyst but it is also of interest because of many other application areas notably as the abrasive in chemical-mechanical planarisation of silicon substrates. Recently, ceria has been the focus of research investigating health effects of nanoparticles. Importantly, the role of non-stoichiometry in ceria nanoparticles is implicated in their biochemistry. Ceria has well understood non-stoichiometry based around the ease of formation of anion vacancies and these can form ordered superstructures based around the fluorite lattice structure exhibited by ceria. The anion vacancies are associated with localised or small polaron states formed by the electrons that remain after oxygen desorption. In simple terms these electrons combine with Ce4+ states to form Ce3+ states whose larger ionic radii is associated with a lattice expansion compared to stoichiometric CeO2. This is a very simplistic explanation and greater defect chemistry complexity is suggested by more recent work. Various authors have shown that vacancies are mobile and may result in vacancy clustering. Ceria nanoparticles are of particular interest because of the high activity and surface area of small particulates. The sensitivity of the cerium electronic band structure to environment would suggest that changes in the properties of ceria particles at nanoscale dimensions might be expected. Notably many authors report a lattice expansion with reducing particle size (largely confined to sub-10 nm particles). Most authors assign increased lattice dimensions to the presence of a surface stable Ce2O3 type layer at low nanoparticle dimensions. However, our understanding of oxide nanoparticles is limited and their full and quantitative characterisation offers serious challenges. In a series of chemical preparations by ourselves we see little evidence of a consistent model emerging to explain lattice parameter changes with nanoparticle size. Based on these results and a review of the literature it is worthwhile asking if a model of surface enhanced defect concentration is consistent with known cerium/cerium oxide chemistries, whether this is applicable to a range of different synthesis methods and if a more consistent description is possible. In Chapter one the science of cerium oxide is outlined including the crystal structure, defect chemistry and different oxidation states available. The uses and applications of cerium oxide are also discussed as well as modelling of the lattice parameter and the doping of the ceria lattice. Chapter two describes both the synthesis techniques and the analytical methods employed to execute this research. Chapter three focuses on high surface area ceria nano-particles and how these have been prepared using a citrate sol-gel precipitation method. Changes to the particle size have been made by calcining the ceria powders at different temperatures. X-ray diffraction methods were used to determine their lattice parameters. The particles sizes were also assessed using transmission electron microscopy (TEM), scanning electron microscopy (SEM), and BET, and, the lattice parameter was found to decrease with decreasing particle size. The results are discussed in light of the role played by surface tension effects. Chapter four describes the morphological and structural characterization of crystalline CeO2 nanoparticles prepared by forward and reverse precipitation techniques and compares these by powder x-ray diffraction (PXRD), nitrogen adsorption (BET) and high resolution transmission electron microscopy (HRTEM) analysis. The two routes give quite different materials although in both cases the products are essentially highly crystalline, dense particulates. It was found that the reverse precipitation technique gave the smallest crystallites with the narrowest size dispersion. This route also gave as-synthesised materials with higher surface areas. HRTEM confirmed the observations made from PXRD data and showed that the two methods resulted in quite different morphologies and surface chemistries. The forward route gives products with significantly greater densities of Ce3+ species compared to the reverse route. Data are explained using known precipitation chemistry and kinetic effects. Chapter five centres on the addition of terbia to ceria and has been investigated using XRD, XRF, XPS and TEM. Good solid solutions were formed across the entire composition range and there was no evidence for the formation of mixed phases or surface segregation over either the composition or temperature range investigated. Both Tb3+ and Tb4+ ions exist within the solution and the ratios of these cations are consistent with the addition of Tb8O15 to the fluorite ceria structure across a wide range of compositions. Local regions of anion vacancy ordering may be visible for small crystallites. There is no evidence of significant Ce3+ ion concentrations formed at the surface or in the bulk by the addition of terbia. The lattice parameter of these materials was seen to decrease with decreasing crystallite size. This is consistent with increased surface tension effects at small dimension. Chapter six reviews size related lattice parameter changes and surface defects in ceria nanocrystals. Ceria (CeO2) has many important applications, notably in catalysis. Many of its uses rely on generating nanodimensioned particles. Ceria has important redox chemistry where Ce4+ cations can be reversibly reduced to Ce3+ cations and associated anion vacancies. The significantly larger size of Ce3+ (compared with Ce4+) has been shown to result in lattice expansion. Many authors have observed lattice expansion in nanodimensioned crystals (nanocrystals), and these have been attributed to the presence of stabilized Ce3+ -anion vacancy combinations in these systems. Experimental results presented here show (i) that significant, but complex changes in the lattice parameter with size can occur in 2-500 nm crystallites, (ii) that there is a definitive relationship between defect chemistry and the lattice parameter in ceria nanocrystals, and (iii) that the stabilizing mechanism for the Ce3+ -anion vacancy defects at the surface of ceria nanocrystals is determined by the size, the surface status, and the analysis conditions. In this work, both lattice expansion and a more unusual lattice contraction in ultrafine nanocrystals are observed. The lattice deformations seen can be defined as a function of both the anion vacancy (hydroxyl) concentration in the nanocrystal and the intensity of the additional pressure imposed by the surface tension on the crystal. The expansion of lattice parameters in ceria nanocrystals is attributed to a number of factors, most notably, the presence of any hydroxyl moieties in the materials. Thus, a very careful understanding of the synthesis combined with characterization is required to understand the surface chemistry of ceria nanocrystals.