Matemaattis-luonnontieteellinen tiedekunta
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(Helsingin yliopisto, 2017)Nanowires (NWs) and nanotubes (NTs) are considered to be of great importance for future nanotechnology applications, due to the roles of dimensionality and small system size. Potential applications of NWs and NTs range from field-effect transistors to biological applications. However, the one-dimensional (1D) nanostructures and most of their applications are still in an early stage of technical development. There are several issues that need to be addressed before they are ripe for industrial applications. Irradiation has been widely used in semiconductor industry to modify the properties of materials since the 1950s. Irradiation in 1D nanomaterials has been studied to tailor the mechanical, electronic, optical and even magnetic properties in a controlled manner, to improve the functionality of the devices based on the 1D nanomaterials. This thesis focuses on the structural and mechanical modifications of the 1D nanomaterials under energetic ion irradiation, as well as the formation mechanisms of the composites of the functional one-dimensional nanomaterials to improve their usage. In the first part, we studied the defect production of GaN NWs under Ar irradiation. The difference of defect production between NWs and the bulk counterpart was studied. The effect of the large surface-area-to-volume ratio was found to play an importance role in defect production in NWs. The irradiation energy of the maximum damage production in the NWs has been obtained. In the second part of the thesis, we studied the formation of the composite nanomaterials of diamond-like-carbon (DLC) and carbon nanotubes (CNTs). We used the classical MD method to simulate the deposition process of carbon atoms on the CNT systems to provide the atomic insights into structural changes. The results show that high-sp$^3$-content DLC can be formed provided the deposition conditions allow for sidewards pressure to form from a substrate close beneath the CNTs.
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(Helsingin yliopisto, 2017)Defects always exists in a crystal lattice at temperatures above absolute zero. Our knowledge of defect concentration and mobility is crucial, due to their profound influence on the material properties. It has been shown that the presence of light impurities may enhance vacancy formation in many metals and metal alloys. The main reason for this phenomenon, often referred to as the superabundant vacancy formation, is the lowering of the vacancy formation energy due to the impurity trapping. In this thesis a theoretical thermodynamics model has been developed to study the equilibrium vacancy concentrations as a function of impurity concentration and temperature. The diffusion of monovacancies and hydrogen in tungsten is studied due to its relevance to fusion research. The molecular dynamics method has been used to simulate the diffusion of hydrogen and monovacancies in tungsten. The commonly accepted and so far used H diffusion migration barrier is revised and a new analysis method to determine diffusion coefficients that accounts for the random oscillation of atoms around the equilibrium position is presented. The results show the presence of multiple nearest neighbour jumps of monovacancy above 2/3 of the melting temperature of tungsten, that partly explains the upward curvature of Arrhenius diagram of self-diffusion experiments in tungsten. For the first time, the W monovacancy diffusion prefactor is calculated, and found to be unexpectedly high, resulting in a monovacancy diffusion attempt frequency of about 2-3 orders of magnitude higher than the values commonly used. A comparative study between the molecular dynamics and a Monte Carlo method – binary collision approximation has been carried out by simulating the single ion impacts on silicon and tungsten surfaces. The results from both methods are compared and found to be in a good agreement for crystalline structures. However, large discrepancies between the two methods arise for materials that are amorphous or become amorphized during ion irradiation.
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(Helsingin yliopisto, 2017)Wind gusts, which are short duration (typically 3 s) wind speed maxima, are representative of the extreme wind conditions. They are very important for human activity, because the strongest gusts associated with storms are the most significant single cause of natural hazards. The impact of wind gusts on different structures depends on the characteristics of each structure. For example for wind energy, it is important to know both the probability of extreme maximum gusts in time scales of decades for the design of power plants and in the shorter term to support wind turbine operations. For wind gust forecasting it is essential to have reliable wind gust observations. Traditionally, observations have only been available from weather stations where the wind is usually measured at a reference height of 10 m. For wind energy, information is needed at greater heights, as the hub heights of the largest turbines extend even above 150 m. The main aim of this work has been to investigate wind gusts across the entire atmospheric boundary layer based on observations from tall meteorological masts as well as applying new measurement methods developed in this dissertation. The novel methods are based on turbulence measurements taken on board a research aircraft and by a Doppler lidar. The research aircraft can fly long distances in a short time, so the measured wind speeds do not represent wind speed variation in time but they are a function of flight distance. The new method developed in this dissertation to compare temporal and spatial scales allows the measurement of wind gusts from a research aircraft. Then, observations can be obtained from places where traditional weather stations or meteorological masts cannot be deployed. Applying the new method, the observed wind gusts from the marine Arctic matched well with those observed at a meteorological mast in the Baltic Sea, although also differences were observed between these environments. Doppler lidar provides radial wind speed measurements along a laser beam transmitted by the instrument. When data from at least three lines of sight are combined, the three-dimensional wind vector can be derived. However, the measurements from multiple lines of sight take several seconds, and the different beams represent different measurement volumes. For these reasons, the measured wind speed maxima from the Doppler lidar used in this work were higher than the corresponding wind gusts from the nearby meteorological mast. In this dissertation, we developed a new theoretical method that significantly reduced this positive bias. Wind gust measurements are usually prone to measurement errors, called outliers. The use of a spike removal algorithm typically applied in traditional turbulence measurements, resulted in significantly improved Doppler lidar data quality. The method performed even better than the traditional data quality assurance methods based on carrier-to-noise ratio, by removing the unrealistic outliers present in the time series. Based on the above wind gust measurements, it was found that in the lowest part of the atmospheric boundary layer the ratio of the wind gust speed and the mean wind speed, called the gust factor, decreases strongly with measurement height. The higher the aerodynamic roughness of the surface, the greater is the change. Moreover, the static stability of the atmosphere affects the gust factor: the decrease of the gust factor with height is clearly smaller in unstable than in stable conditions. The gust parameterizations used in numerical weather prediction models were originally designed for the reference measurement height of 10 m. A new parameterization was developed that takes into account not only the effects of surface roughness and atmospheric stability but also the height above the surface. Based on meteorological mast and research aircraft measurements, the new parametrization yielded better results than previous methods.
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(Helsingin yliopisto, 2017)This study, positioned in the fields of humanistic geography and young people’s geographies, deals with young people’s place experiences in the city. I consider such experiences subjective, and study place from the perspective of personal relations and experienced insideness and outsideness. I also understand place as an intersubjective experience comprising social encounters. My research contributes to the literature on mobility, specifically in examining place from the perspective of daily mobility and personal networks. The participants were young people in upper-secondary education in the Helsinki metropolitan area, Finland. The research material consists of go-along interviews, photographs, GPS recordings and independent assignments, gathered in accordance with participatory methods. Earlier research findings indicate that adults define and restrict young people’s places in urban space, and that their experiences of insideness and outsideness are strongly elated to other meaningful social encounters. Daily mobility also tends to be perceived as a bodily and routine practice, whereas mobility opportunities are connected to young people’s experienced independence. According to the participants, socio-spatial tensions that typically arise between adults and young people no longer influenced the construction of their place experiences. The meanings of familiar childhood places, used for activities such as hanging out, changed as these young people were more commonly encountered as ‘almost adults’ in different places. Childhood places still evoked strong memories, but were no longer at the centre of daily life. They still had a significant bridge-building role in reconciling memories of familiar childhood places with contradictory experiences of new adulthood places. Thus, I claim that young people are experientially living between their childhood and adulthood places, actively constructing new personal places in their everyday environments in the process of growing up. The young people emphasised the importance of friends in fostering feelings of insideness with place. Groups of friends had their private ‘our’ places, but also more open places in which ‘they’ were welcome. Meetings with ‘them’ were easier if friends were present. Social encounters sometimes evoked strong feelings of outsideness despite the presence of friends, however, especially if such feelings were shared. Nevertheless, those who had the skills and resources to handle experiences related to encounters with different people in their daily places seemed to retain their feelings of insideness. My findings reveal that the construction of (inter)subjective meanings of places is tightly intertwined with daily mobility. The young people described how daily moving structured the experiential and bodily connections between them and their places, supporting their way of living and being in the city and enabling them to practise new adulthood. They had plenty of freedom related to daily, bodily mobility, and were restricted by a poor public-transport network, and the lack of a driving licence and vehicle, rather than parental strictures. Daily places form webs of meaningful places and experienced (dis)connections between places and people, in which (inter)subjective meaning-making is intermingled with daily mobilities. Given that experienced disconnections appear to arouse feelings of outsideness, young people should learn to recognize their experiential ties with places and handle the breakages. To do this they need places that support their everyday agency in terms of actively influencing their personal connections with places and promoting feelings of insideness. Keywords: young people, place experiences, place, everyday life, urban space
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(Helsingin yliopisto, 2017)The aim of this work was to study the climate change impact on two specific abiotic risks affecting forests in Finland: fires and heavy snow loads. Approximately 1000 forest fires occur annually in Finland, but thanks to effective fire suppression, the average size of fires is only about 0.5 ha. Occasionally, heavy snow loading causes forest damage, which reduces stand quality in boreal forests experiencing cold winters. In Finnish forests, snow damage occurs most commonly in the eastern and northern parts of the country. The basic tools used in this work to evaluate the climate change impact were climate models. In addition, observational weather data and fire statistics were used. In evaluating the forest fire risk, the Canadian Fire Weather Index (FWI) system was used. Snow load amounts were estimated mainly by applying a snow load model developed at the Finnish Meteorological Institute (FMI). The results indicate that forest fire risk will most likely increase in the future due to increasing temperature and enhanced evaporation. However, there is large uncertainty regarding the rate of change, which originates from the differences between climate model responses to the same radiative forcing. Moreover, an increase in forest fire risk will at the same time increase the risk of conflagrations. Crown snow loads were projected to become heavier in northern Finland and in the regions of Kainuu and North Karelia next to the Russian border. In southern and western Finland the risk of snow damage is expected to decrease. The largest decrease in the risk is projected to occur in coastal areas. In the areas expected to experience increased risk of snow damage, conditions favouring both heavy wet snow loading and rime accretion were predicted to become more common. The results of this work can be utilized when considering climatically-driven risks in forest management.
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(Helsingin yliopisto, 2017)Electrical impedance tomography (EIT) is a rather new approach to medical imaging that is motivated by using electricity to determine the inside of a body. The clear advantage lies in the usage of harmless electric currents, in contrast to the ionizing radiation of X-rays, whereas the mathematical problem is inherently more challenging. In EIT we seek to reconstruct an image of the inner organs by determining their conductivity, i.e. how well electricity is conducted. As a medical imaging modality it is most promising in pulmonary and cardiac imaging, due to considerably different conductivity values in the air filled lungs (low conductive) and the blood filled heart (high conductive). EIT is in principle capable of monitoring the respiratory process, detecting pathologies in the lungs, and monitoring the heart activity. The main focus of this work is on the partial-boundary problem in EIT, that means one has only access to a certain part of the boundary and data can only be collected there. In a hospital setting these situations can arise when monitoring a critical or unconscious patient and hence one can only access the front of the torso (ventral position). Furthermore, practical complications can arise due to faulty, dislocated, or dispatched electrodes and hence leading to incomplete data. The methods presented in this thesis are capable of dealing with such incomplete data. Following the tradition of mathematical research we are also interested in quantifying the error incomplete data introduces to the reconstruction. In a short summary, this thesis investigates how to improve EIT reconstructions from partial-boundary data by utilizing concepts from an ideal mathematical setting as well as how to apply these methods to real electrode models and measurement data.
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(VTT, 2017)Currently, the preferred option for the long-term disposal of spent nuclear fuel (SNF) and potentially for future thorium-based fuels in Finland and Sweden is disposal in a geological repository. In deep bedrock, the release of Th, U and other radionuclides through man-made barriers and the geo- and biosphere will be controlled by the dissolution of the fuel by groundwater. Thorium dioxide is isostructural to uranium dioxide, sharing the same fluorite structure (space group Fm3m) and making it a useful analogue material for nuclear fuel, which mainly consists of UO2 (>95%). This thesis aimed to investigate the dissolution of ThO2, which was synthesised to approximate as closely as possible the microstructure of UO2 in a nuclear fuel matrix. The investigation consists of dissolution studies conducted using pellets, fragments (2 to 4 mm) and particles (80 to 160 µm) of 232ThO2. The evolution of dissolving surfaces and grain boundaries were examined by combining different microscope imaging techniques (scanning electron microscopy (SEM), atomic force microscopy (AFM), SEM with electron backscattering diffraction detector (SEM-EBSD) and profilometer imaging). Part of the dissolution experiments were conducted in the presence of a 229Th tracer to gain additional data on the dissolution and precipitation by following the change in isotopic ratio 229Th/232Th. Furthermore, the pellets from these experiments were measured with direct alpha spectrometry to estimate the contents and thickness of the 229Th-rich layer formed on the pellet surface. The results of all dissolution studies showed a relatively fast release of thorium during the early stage of the experiment followed by a slow decrease in the thorium concentration and suppression of the dissolution rate as the experiments continued over 100 days. Microscopic studies revealed that the grain boundaries play a significant role in the initial release of thorium. It was also observed that the different surfaces of thorium dioxide particles behave differently either dissolving, precipitating or showing an almost inert nature, most likely due to the different surface energies of the heterogeneous material. High-resolution (sector field) inductively coupled plasma mass spectrometry (SF/HR-ICP-MS) was used for the thorium isotope analyses of leached solutions. The developed method was powerful for analysing thorium isotopes. In addition, alpha spectrometry was used for thorium analysis for comparative purposes. The alpha spectrometry yielded a lower detection limit for 229Th and a higher detection limit for 232Th than SF-ICP-MS, which was 1 x 10-12 mol for both isotopes. Thus, these methods provided comparable results for the analysed 229Th concentration. However, the chemical separation needed before alpha spectrometry is very time consuming compared to the sample preparation necessary for HR-ICP-MS. When combined with simulations, direct alpha analysis confirmed that during leaching a new layer, with a maximum thickness of 0.1 µm, formed on the surface of ThO2 pellets. Alpha spectrometry also provided interesting insight into the dissolution and co-precipitation behaviour of 229Th and 232Th decay series daughter nuclides. The surface layer contained not only 229Th and its daughters, but also an elevated concentration of daughters from the 232Th decay series, indicating that they were first released from the bulk during the leaching experiment, subsequently co-precipitating or adsorbing onto the surface of the pellet.
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(Helsingin yliopisto, 2017)The current era of bioeconomy strives to develop new, innovative products from natural raw materials in a sustainable way. In this PhD thesis, we have searched potential bioactive compounds from different parts of the neglected roots and stumps of conifer trees for high value products. Our aim was to establish deeper knowledge concerning chemical compositions of specified and defined biomass sources (roots and stumps of conifer trees) as well as the chemistry of certain natural polyphenolic compounds in different conditions. Using methods of natural products chemistry, such as solvent extraction and chromatographic separation and analysis techniques (GC-MS, HPLC-DAD/MS), we found that the root bark of Norway spruce is a rich source of stilbenoid glucosides (astringin, isorhapontin and piceid). These have structural similarities with the most studied stilbenoid, resveratrol. We also found that the stumps of Scots pine are a source of stilbenoids, pinosylvin and its derivatives. Stilbenoids are bioactive compounds and they have shown a variety of beneficial activities in studies related for example to human health. They have also shown antimicrobial and protective properties in trees and also in tests against micro-organisms. The highest concentrations of stilbenoid glucosides were found from the inner bark of the root zones closest to the stem of Norway spruce. This study also revealed that the root neck of Norway spruce is a new source of the bioactive lignan hydroxymatairesinol (HMR). Chromatographic and spectroscopic methods were developed to isolate pure stilbenoids from the bark of Norway spruce roots for further experiments. The complete structural elucidation of stilbenoids from Norway spruce was performed by HPLC-DAD-NMR. The HPLC-DAD method was further optimized to isolate stilbenoids in a semipreparative scale. The invividual stilbenoid molecules were isolated from the extracts and their photochemical stabilities (under fluorescent and UV light) were studied by HPLC-DAD, MS and NMR. Naturally-occurring trans stilbenoids undergo photochemical transformations to cis forms. However, the extended UV irradiation caused stilbenoids to form phenanthrene structures by intramolecular cyclisation. This is the first time that these new phenanthrene structures are reported to be derived from stilbenoids of spruce bark. Our results show that that the roots and stumps of conifer trees contain bioactive polyphenolic compounds, such as stilbenoids and lignans. These molecules and the compounds formed thereof may have commercial value and the information gained would offer a base platform for the possible new commercial high-value products developed from forest biomass. Our study has also provided new scientific knowledge of natural compounds and their properties that may lead to new findings and deeper understanding of the physiology and internal protection processes of plants by their bioactive secondary metabolites. Roots and stumps of conifer trees (Norway spruce and Scots pine) are a vast source of biomass containing potentially bioactive polyphenolic extractives as shown in this work, but this biomass is currently used for low-value energy production only. With already existing harvesting techniques, roots and stumps of conifer trees could be used as a source of commercially valuable biochemicals.
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(Helsingin yliopisto, 2017)Visual attention is crucial in mobile environments, not only for staying aware of dynamic situations, but also for safety reasons. However, current mobile interaction design forces the user to focus on the visual interface of the handheld device, thus limiting the user's ability to process visual information from their environment. In response to these issues, a common solution is to encode information with on-device vibrotactile feedback. However, the vibration is transitory and is often difficult to perceive when mobile. Another approach is to make visual interfaces even more dominant with smart glasses, which enable head-up interaction on their see-through interface. Yet, their input methods raise many concerns regarding social acceptability, preventing them from being widely adopted. There is a need to derive feasible interaction techniques for mobile use while maintaining the user's situational awareness, and this thesis argues that solutions could be derived through the exploration of hand-based haptic interfaces. The objective of this research is to provide multimodal interaction for users to better interact with information while maintaining proper attention to the environment in mobile scenarios. Three research areas were identified. The first is developing expressive haptic stimuli, in which the research investigates how static haptic stimuli could be derived. The second is designing mobile spatial interaction with the user's surroundings as content, which manifests situations in which visual attention to the environment is most needed. The last is interacting with the always-on visual interface on smart glasses, the seemingly ideal solution for mobile applications. The three areas extend along the axis of the demand of visual attention on the interface, from non-visual to always-on visual interfaces. Interactive prototypes were constructed and deployed in studies for each research area, including two shape-changing mechanisms feasible for augmenting mobile devices and a spatial-sensing haptic glove featuring mid-air hand-gestural interaction with haptic support. The findings across the three research areas highlight the immediate benefits of incorporating hand-based haptic interfaces into applications. First, shape-changing interfaces can provide static and continuous haptic stimuli for mobile communication. Secondly, enabling direct interaction with real-world landmarks through a haptic glove and leaving visual attention on the surroundings could result in a higher level of immersed experience. Lastly, the users of smart glasses can benefit from the unobtrusive hand-gestural interaction enabled by the isolated tracking technique of a haptic glove. Overall, this work calls for mobile interaction design to consider haptic stimuli beyond on-device vibration, and mobile hardware solutions beyond the handheld form factor. It also invites designers to consider how to confront the competition of cognitive resources among multiple tasks from an interaction design perspective.
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(Helsingin yliopisto, 2017)This thesis is motivated by two important processes in bioinformatics, namely variation calling and haplotyping. The contributions range from basic algorithms for sequence analysis, to the implementation of pipelines to deal with real data. Variation calling characterizes an individual's genome by identifying how it differs from a reference genome. It uses reads -- small DNA fragments -- extracted from a biological sample, and aligns them to the reference to identify the genetic variants present in the donor's genome. A related procedure is haplotype phasing. Sexual organisms have their genome organized in two sets of chromosomes, with equivalent functions. Each set is inherited from the mother and the father respectively, and its elements are called haplotypes. The haplotype phasing problem is, once genetic variants are discovered, to attribute them to either of the haplotypes. The first problem we consider is to efficiently index large collections of genomes. The Lempel-Ziv compression algorithms is a useful tool for this. We focus on two of its exponents, namely the RLZ and LZ77 algorithms. We analyze the first, and propose some modifications to both, to finally develop a scalable index for large and repetitive collections. Then, using that index, we propose a novel pipeline for variation calling to replace the single reference by thousands of them. We test our variation calling pipeline on a mutation-rich subsequence of a Finnish population genome. Our approach consistently outperforms the single-reference approach to variation calling. The second part of this thesis revolves around the haplotype phasing problem. First, we propose a generalization of sequence alignment for diploid genomes. Next we extend this model to offer a solution for the haplotype phasing problem in the family-trio setting (that is, when we know the variants present in an individual and in her parents). Finally, in the context of an existing read-based approach to haplotyping, we go back to basic algorithms, where we model the problem of pruning a set of reads aligned to a reference as an interval scheduling problem. We propose a exact solution that runs in subquadratic time and a 2-approximation algorithm that runs in linearithmic time.
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(Helsingin yliopisto, 2017)Northern lakes are displaying widespread ecological reorganizations in response to global change. These sensitive freshwater ecosystems are an integral component of subarctic and arctic landscapes and play a critical role in regional and global biogeochemical cycles. To understand lake ecosystem responses to direct and indirect climate forcing, and to estimate future trajectories of environmental change, we must look for past analogies of climate-lake interaction recorded in lake sedimentary archives. The present, in turn, holds the key to understand the past. This work examines patters and drivers of limnoecological change in shallow subarctic lakes across the treeline ecotone in northern Finland. A diverse set of neolimnological and paleolimnological tools and approaches were employed to explore aquatic ecosystem responses to landscape variability and direct climate forcing through space and time. Particular emphasis was placed on aquatic organic carbon that regulates vital biogeochemical processes in lakes and couples them to the global carbon cycle. To address landscape-mediated climate impact on shallow subarctic lakes, catchment controls on pelagic (lake water) and benthic (sediment) carbon pools, nutrients and productivity, periphytic algal (diatom) communities, and carbon utilization of benthic macrofauna (Cladocera) were assessed in 31 lakes spanning the treeline. To investigate long-term ecosystem development and carbon dynamics under natural and anthropogenic climate variability, two downcore sediment sequences from shallow and oligotrophic treeline lakes, covering the postglacial period (~11 500 years) and the late neoglacial (~600 years), were examined for diverse biogeochemical and paleobiological indices. Across the treeline, lake water carbon pools were fundamentally shaped by wetland influence. The adverse effect of terrestrial colored organic carbon on underwater light availability was diminished in the shallow waters and superseded by nutrient stimulation of primary production. Catchment and soil geomorphology and related hydrological processes were further identified as important controls over aquatic carbon pools, nutrient regimes, and lake water acid-base balance, carrying effects on aquatic primary production and diatom community structure. The late neoglacial paleolimnological record demonstrated a strong coupling between centennial temperature fluctuations, the structure and productivity of aquatic communities, and carbon sequestration. The changes were attributed primarily to alterations in the length of the ice cover period, and were most distinct over the Anthropocene. The postglacial sediment sequence demonstrated repeated diatom turnovers over the Holocene, attributed primarily to millennial moisture fluctuations driving changes in the depth and turbulence of the water column. Overall, the results strengthen recent notions related to the strong terrestrial-aquatic coupling as well as to the susceptibility of northern lakes to climate change, providing new aspects into the underlying processes, drivers of heterogeneity, and biotic interactions. Collectively, the findings build towards an improved understanding of the responses and resilience of northern lake ecosystems to a hierarchy of environmental drivers under the ongoing global change.
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(Helsingin yliopisto, 2017)This thesis investigates the cross-sectional association between different quantifiable societal dimensions that indicate spatially varying levels of wellbeing and development. The analysis is grounded in human geography but applies an explicitly interdisciplinary focus, combining theories and measures from economic geography, cultural studies, spatial economics, sociology and social psychology. In the empirical analyses, geographically referenced European Social Survey (ESS) data containing measures of subjective wellbeing (SWB) and human values were analysed together with objective indicators of economic performance on national and subnational scales. First, Paper I demonstrated that levels of ‘social trust’ and ‘social contact and support’, which indicate social wellbeing, and a sense of ‘competence and meaning’, which denotes personal wellbeing, are significant positive correlates with regional GDP after controlling for regional economic indicators and the spatial effects embedded in the data. Second, Paper II utilized the Human Values Scale in the ESS and studied the association between certain values and the level of economic performance. The paper demonstrated that the aggregate level of the value ‘self-direction’, which indicates independent thought, action and creativity, is a strong predictor of regional GDP. Paper II also addressed the question of rescaling and used welfare regimes as a relevant socio-historic framework of analysis. Paper III focused on the contextual effects of living in ‘Metropolitan Finland’. The results showed that the negative effect on life satisfaction of residing in the capital region of Finland is first compositional, as the population in ‘Metropolitan Finland’ is composed of individuals who appreciate the values of ‘power’ and ‘achievement’, which are themselves associated with lower life satisfaction. However, it is also contextual, as residing in the capital region moderates the positive wellbeing effect of socially focused values such as ‘benevolence’ and ‘conformity’. Finally, Paper IV added vertical detail to the intercept heterogeneity approach and asked whether changes in macroeconomic conditions, in the context of Ireland and its recent economic recession, are experienced differently in different socio-economic categories, i.e. classes. The results show that the effects of the economic crisis were not experienced equally within the population; rather, the lower strata (the lowest income quartile, manual workers and those with the lowest levels of education) were the most affected. Both the framework and results of this thesis offer new interdisciplinary insights into the geographies of subjective wellbeing and human values, a disciplinary interface that has largely remained unexplored. The results of this thesis are also relevant for regional policy-making that addresses spatial justice, territorial inequalities and uneven development. Furthermore, the findings concerning the negative wellbeing effect of metropolitan context merit attention in policies on ‘urban growth’, as they question the underlying values of such policies and their effectiveness for promoting wellbeing. Finally, the finding that macroeconomic changes have different wellbeing effects in different socio-economic layers resonates with the concept of ‘inclusive growth’, which involves promoting the distribution of opportunities and wellbeing to all segments of the population.
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(Helsingin yliopisto, 2017)Both atmospheric ice and mineral dust are considered to play important roles in our climate system through their impacts on the radiative energy budget. These impacts depend on the size, shape, composition and concentration of the ice and dust particles. However, the non-spherical shape of these particles yields uncertainties in our understanding how they interact with radiation. One of the main aims of this work is to better understand the impacts of particle size-shape distributions on radiative effects of ice and dust. For dust particles, the overall goal is to improve the treatment of optical properties of dust in global aerosol-climate models. In this thesis, the solar radiative effects of variously sized and shaped ice and dust particles are simulated using radiative transfer models. In addition, a global aerosol–climate model is used to investigate the impact of dust particle nonsphericity. Different radiative transfer models, atmospheric and surface properties etc. are used, based on the requirements of each study. Size-shape distributions of ice clouds are based on in-situ measurements, whereas for dust, carefully validated shape models of spheroids are used. This thesis offers a broad outlook on the effects of ice clouds on solar irradiances and on the angular dependence of the circumsolar radiance. In addition, it offers interesting new insight into the connections between particle morphology, cloud microphysics and cloud radiative effects. It is found that solar radiation is sensitive to the concentration of small ice crystals. In addition, comparison of simulated and measured radiation in the presence of ice clouds suggests that most natural ice crystals are not pristine, but can either have some surface roughness or other non-idealities in their shape. The results reveal that the use of spheroidal shape distributions has only small or moderate impacts on regional and global-scale direct radiative effects of dust. Consistent with this, experiments with a global aerosol–climate model indicate that the assumption of spherical shape for dust particles is not a considerable error source in climate simulations. Most probably, however, this conclusion cannot be extended to remote sensing applications. Keywords: ice crystal, mineral dust, single-scattering properties, solar radiation, circumsolar radiation, radiative transfer modelling, spheroids
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(Helsingin yliopisto, 2017)The increasing interest in both portable electronic devices and electric vehicles has given rise to a new wave of research into lithium-ion batteries. Lithium-ion batteries are the technology of choice for these applications, as they offer both high power and high energy densities. However, much research on this subject is still needed to answer the technology demands of future applications. For example, the safety concerns related to liquid electrolytes in the batteries of electric vehicles could be resolved by moving to all-solid-state batteries, which would not combust in the case of an accident. In addition, all-solid-state batteries could be manufactured into 3D structures, which would decrease the footprint area of the battery without sacrificing the amount of material. Thus, these structures would make even higher energy densities possible, which is important for example for laptops and cellphones. In addition, by combining smaller batteries with energy harvesters, such as solar cells, integrated autonomous devices could be realized. Atomic layer deposition, or ALD, is a thin film deposition method based on sequential, saturative reactions of gaseous precursors with a substrate surface. ALD generally produces highly pure films with very good thickness uniformity also in difficult, 3D substrates. Therefore, ALD should be well-suited for the deposition of Li-ion battery materials for future applications. The deposition of lithium containing materials is a fairly new avenue for ALD, the first paper being published only in 2009. It has been found that the Li-ion often bends the basic rules of ALD with its high reactivity and mobility during film growth, resulting in both unexpected reactions and film stoichiometries. This thesis provides a comprehensive review on the atomic layer deposition of lithium containing materials with a focus on the behavior of lithium in the growth process. In the experimental part, new ALD processes were developed for potential Li-ion battery materials LiF and AlF3. Both processes show reasonable ALD characteristics and produce pure films in proper deposition temperatures. In addition, conversion reactions taking place in ALD conditions were studied, and both LiF and Li3AlF6 were deposited using these reactions. The conversions were very clean, illustrated by the low impurity contents of the converted films. Lastly, the deposition of lithium containing ternary oxides was studied by heating atomic layer deposited film stacks in air. This ALD-solid state reaction -procedure resulted in pure, crystalline films of LiTaO3, LiNbO3 and Li2TiO3.
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(Helsingin yliopisto, 2017)This dissertation belongs to the field of harmonic analysis, which is a subfield of mathematical analysis. It consists of an introductory part and four research articles. Two of the articles study testing characterizations of two-weight inequalities and the other two study local Tb theorems. An operator, such as a singular integral or a dyadic integral operator, satisfies a two-weight inequality if it is bounded between two weighted function spaces Testing characterizations show that to have the two-weight inequality it suffices to test the operator with a very restricted class of functions. Local Tb theorems provide criteria for boundedness of a given operator, usually of a singular integral or a square function. The basic idea is similar to testing of two-weight inequalities: to have boundedness it is enough to test the operator with suitable test functions. Nazarov, Treil and Volberg characterized two-weight inequalities of well localized operators between two L^2-spaces in terms of so-called Sawyer type testing conditions. The first article in the thesis introduces a quadratic testing condition and shows that it can be used in place of the Sawyer type testing condition to obtain an L^p-version of the mentioned L^2-result. The second article introduces a quadratic version of the Muckenhoupt type two-weight A_p condition on the weights. It is shown that if the weights satisfy the quadratic A_p condition, and a dyadic shift operator satisfies the quadratic testing conditions in L^p, then a certain quantitative two-weight estimate holds. This is an L^p-version of the L^2-result by Hytönen, Pérez, Treil and Volberg. The third article introduces a new method to prove local Tb theorems. It relies on ``big piece thinking'', which appears in connection with other problems in mathematical analysis, and on the non-homogeneous good lambda method of Tolsa. By using the new method, the article improves known results concerning local Tb theorems for vertical square functions in the upper half space. The final article studies conical square functions which are defined with respect to a general closed subset of the Euclidean space. The method from the third article is applied to prove a corresponding local Tb theorem in this set-up.
