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  • Ylöstalo, Otto (2020)
    The decathlon is a track and field event that consists of ten single events, which are performed in the same order during two competitive days. The result from each event is according to the official scoring table transformed into points which are then added together and result in the final score. The aim of this study is to see, what makes an elite decathlete. The individual development in each event is observed. For this study material consisting of all recorded data by decathletes with a personal best of over 8 500 points from year 1970 to 2019 have been used. From the data the best (individual) results made within a decathlon per year was chosen up until the best season. Changes in the decathlete´s profile has been analyzed in four stages (clusters). Changes in the individual development pattern based on the initial level in each event is also observed. The theory part covers the linear mixed-effects model introduced by Laird and Ware. The restricted maximum likelihood method related to the model is deduced in detail. According to the results of the study it seems like the sprint events are of great importance in the decathlon. Especially initially weak 400-meter-runners make a notable progress. However, some initially weak events remain relatively weak compared to the initially stronger.
  • Savolainen, Varpu (2023)
    In the industry categorization, construction industry is one of the largest sources of waste and greenhouse gas emissions. Construction industry, with norms, practices, business models, and legislation connected to it, is built on linear foundations. In a linear economy, energy and material flows are based on value addition and a take-make-use-dispose logic. The circular economy is pursued as a replacement to the linear economic model and is based on the idea of value preservation. Among several other sustainability-driven concepts, the use of the concept of circular economy is growing in local, national and international level environmental governance. This thesis is located in the complex and ambiguous conceptual framework of circular economy as a sustainability transformation in municipal politics. The subjects under observation are four Finnish cities: Helsinki, Joensuu, Turku, and Vantaa. I aim to gain an understanding of why circular economy policy implementation in the construction and demolition of buildings seems inadequate in comparison to the municipalities’ circular economy and sustainability ambitions and whether it really is so. The current city strategies, the policy documents with the most significant guiding impact to circular construction, and interviews with experts from the municipalities and construction sector are analyzed with thematic analysis. This thesis is a part of a six-year transdisciplinary research project, DeCarbon-Home, which studies and co-develops solutions to the just sustainability transitions of living and construction. The results of this thesis show that the understanding and awareness of the concept of circular economy and ambitions attached to it vary significantly not only between cities but also within. The cities are in different phases of circular economy transition, and the results demonstrate various pathways of policy implementation. Some shared challenges that are so far hindering the cities from implementing circularity in construction have to do with the lock-in with the current linear system, division of ownership and responsibility, communication, timing, and paradigm shift.
  • Saksala, Teemu Sakari (2013)
    Pro gradu -tutkielman varsinaisena tavoitteena on johtaa Hassler Whitneyn vuonna 1936 alkujaan todistama hänen nimeään kantava Whitneyn upotuslause, jonka mukaan jokainen sileä monisto on diffeomorfinen euklidisen avaruuden jonkin alimoniston kanssa. Työn ensimmäisessä luvussa tutustutaan kolmeen analyysin keskeiseen tulokseen. Nämä ovat Käänteiskuvauslause, Implisiittifunktiolause ja Astelause. Nämä lauseet käsittelevät sileiden kuvausten lokaalien käänteiskuvausten olemassaoloa eri ulotteisissa lähtö- ja maaliavaruuksissa. Näitä kolmea lausetta käytetään seuraavien kolmen luvun aikana useasti. Toisessa luvussa tutustutaan sileiden monistojen teorian perusteisiin. Tässä luvussa määritellään muun muassa seuraavat käsitteet: kartta, sileä kuvaus, tangenttikimppu ja -avaruus, tangenttikuvaukset, immersio sekä alimonisto. Luvun lopussa perehdytään monistojen parakompaktisuuteen ja kehitetään työkaluja, joilla saadaan olemassaolevien karttojen avulla aikaiseksi hyödyllisempiä karttoja. Kolmannessa luvussa osoitetaan, että jokainen kompakti sileä monisto voidaan upottaa sileästi euklidiseen avaruuteen. Tämä antaa aiheen tarkastella tarkemmin euklidisten avaruuksien alimonistojen ominaisuuksia. Lopuksi löydetään tarkka arvo sille, miten moniulotteiseen avaruuteen sileät kompaktit monistot voidaan sileästi upottaa. Työn neljäs luku aloitetaan jatkamalla monistojen parakompaktisuustutkimusta. Luvun ensimmäisen kappaleen tavoitteena on luoda sileitä ykkösen osituksia. Luku jatkuu monistojen nollamittaisten joukkojen käsitteen määrittelemisellä. Luvun lopussa käytetään aikaisemmin luotuja työkaluja hyödyksi ja osoitetaan, että jokaista sileää kuvausta sopivaulotteiseen euklidiseen avaruuteen voidaan approksimoida sileillä injektiivisillä immersioilla. Tämän tuloksen avulla työn päätulos voidaan todistaa kohtalaisen helposti.
  • Milén, Hannu (2023)
    The thesis consists of presenting and analysing the original proof for the Embedding Theorem that Hassler Whitney gave in his 1936 article Differentiable Manifolds. The embedding theorem states that given an m-dimensional Cr-differentiable (r ≥ 1) manifold M, it is possible to embed it in Euclidean space Rn, if n ≥ 2m + 1. Embedding is defined as a mapping f : M → Rn which is Cr-smooth, bijective immersion that is homeomorphism to its image f[M]. Whitney’s proof rests on few important novel concepts and a series of lemmas in relation to them. These concepts include the concept of the k-extent of a set, a sort of a k-dimensional measure in an n-dimensional space; the concept of Cr-function g : M → N approximating (f, M, r, η), where f is a Cr-function f : M → N, η an error function; and the concept of (f, r, η)-properties defined for such g. Outstanding lemmas of general nature are Lemma 7: If f : M → N is a Cr-map and A ⊂ M is of finite (zero) k-extent, then f[A] is of finite (zero) k-extent. Lemma 8: For open sets R and R′ of Rm and Rh, if {Tα} is a h-parameter family of C1-maps of R ⊂ Rm into Rn, and A ⊂ R and B ⊂ Rn closed subsets, such that A is of finite k-extent and B of zero (h − k)-extent, then for some α ∈ R′, Tα[A] does not intersect B. Lemma 9: If f : M → N is a Cr-map, η positive continuous function in M, Ω1, Ω2, . . . are (f, r, η)- properties, then there is a Cr-map F : M → N which approximates (f, M, r, η) and has properties Ω1, Ω2, . . . . Lemmas 11 and 12 then show that bijectivity and immersion property are the logical sum of countable number of (f, r, η)-properties. These facts are used in finding an embedding F : M → Rn by perturbing a given smooth function f : M → Rn. Detailed treatment of all proofs is provided. Adjustments to the proofs are made where deemed necessary; auxiliary assumptions are made where they seem to be required. Clarifications and proofs are given to facts noted but not proven in the article
  • Jossi, Anin (2023)
    Urban development causes a decline of biodiversity, which is alarming as it is crucial for the health of urban nature as well as urban residents. The latter play an important role in the conservation of biodiversity, as they have to accept it. While previous studies have used single attributes and smaller samples to examine whether and how people know about biodiversity, little attention has been paid to place-based perceptions in a more holistic manner at the city level and with including different perception attributes. This study is a secondary analysis of data collected through public participation geographic information system (PPGIS) in Helsinki, Finland, as part of the CO-CARBON project and aims to understand how perceptions of high biodiversity vary between different age groups considering the type of green space, the frequency of access to different green spaces, the distance of perceived high biodiversity from home, and the location of high biodiversity. I analyzed responses of younger (n1 = 290, aged 16-39), middle-aged (n2 = 286, aged 40-52), and older (n3 = 283, aged 53-98) residents of Helsinki using geographical information systems (QGIS and ArcGIS) for spatial and statistical package for social sciences (SPSS) for non-spatial analyses. Statistical significances of the different variables were tested with multivariate analysis of variance (MANOVA), Chi-square tests, Spearman rho, and optimized hotspot analysis. Some differences, but also similarities, could be found between age groups in their perception of high biodiversity. The age groups are similar in the number of mapped points in terms of green space type, as they mostly perceived natural green spaces as high in biodiversity, but older people differed from the others in terms of frequency of access to green space types, while younger people differed in terms of marking high biodiversity further away from home. Notably, all age groups perceived central bigger green areas, especially Vanhankaupunkilahti, the most as high in biodiversity. Younger people formed the most spatial hotspots of perceptions of high biodiversity, as well as a coldspot at Malmi airport, while the oldest age group formed the fewest hotspots. As a consequence of these results, I discuss and conclude what measures through which media tools could be taken in order to achieve more knowledge and involvement of biodiversity conservation. Further research on perception of biodiversity will benefit from understanding what was understood to be biodiverse at the mapped location, examining other groups, studying effective communication of biodiversity issues and conservation events, looking at biodiversity opposed to high biodiversity, and examining the biodiversity perception of wetland and urban green spaces in more detail.
  • Hakanen, Johanna (2020)
    The liberal peace paradigm focusing on a top-down approach and implementing Western values in a one-fits-all model dominated the field of peacekeeping and crisis management missions especially from the 1980s onwards. Later, local ownership became a “buzzword” in international interventions after some major failures of peacekeeping missions in the 1990s and early 2000s. Since then highlighting the relevance of the inclusion of local actors and of utilizing local knowledge have become inseparable parts of the major international organizations’ policy documents and strategies dealing with crisis management and peacebuilding. However, the definition of who or where is local has not been adequately addressed. This has led to using the local as a concept referring to almost anything and everything within the borders of a state. The vague conceptualization has been criticized by scholars, as it leaves unanswered many questions about who can represent local interests or which actors should be included in a crisis management process to increase the sustainability of the intervention. This Master’s thesis seeks research on who, what or where the local level is seen to be in the context of the EU’s civilian crisis management. It does it by uncovering and discussing discourses of the local level from a set of the EU’s documents dealing with civilian crisis management or external action more generally. In this thesis the local level is framed as a social construction through the notion of scale and level from human geographical literature. The human geographical literature also highlights the importance of not only looking at the discourses of the local level but also how it relates to other levels to gain a fuller understanding. The thesis also discusses the potential political opportunity structures that follow from these discourses. There are three main discourses found in the documents focusing on who the local level comprises of: authorities and government, civil society and a variety of different actors on different levels within the nation. None of these discourses raises above the others. Instead, they co-exist, leaving the local level vaguely defined. It is argued that this gives the EU an opportunity to pick the local actors to cooperate with case-by-case. This choice can reflect the needs and will of the EU, the host country or both. In addition, two discourses relating to what the local level represents more generally were discovered. These form a dichotomy: the local is seen both as a threat to the security of the EU citizens but simultaneously as a necessity to include in missions to increase the effectiveness of CSDP missions. Overall, the importance of local ownership is highlighted throughout the documents. Considering this, the low level of mentions of local actors is somewhat surprising as well as the vague definition of who or where is local.
  • Xu, Lilu (2013)
    WikiMage is an online web game based on Wikipedia which is a free, collaboratively edited, and multilingual Internet encyclopedia. The name WikiMage is a combination of Wikipedia and Image that implies the game is built on those images referenced by Wikipedia articles. The WikiMage will challenge the players in terms of their width and depth of knowledge. During the game, a large number of pictures will be presented, and only the player who is able to distinguish the potential relationships between those images can win the game. It is deployed in CoSCo Demos server. By the time this article is composed, WikiMage is accessible through its URL.
  • Lauri, Tuomo (Helsingin yliopistoHelsingfors universitetUniversity of Helsinki, 2010)
    This study evaluates how the advection of precipitation, or wind drift, between the radar volume and ground affects radar measurements of precipitation. Normally precipitation is assumed to fall vertically to the ground from the contributing volume, and thus the radar measurement represents the geographical location immediately below. In this study radar measurements are corrected using hydrometeor trajectories calculated from measured and forecasted winds, and the effect of trajectory-correction on the radar measurements is evaluated. Wind drift statistics for Finland are compiled using sounding data from two weather stations spanning two years. For each sounding, the hydrometeor phase at ground level is estimated and drift distance calculated using different originating level heights. This way the drift statistics are constructed as a function of range from radar and elevation angle. On average, wind drift of 1 km was exceeded at approximately 60 km distance, while drift of 10 km was exceeded at 100 km distance. Trajectories were calculated using model winds in order to produce a trajectory-corrected ground field from radar PPI images. It was found that at the upwind side from the radar the effective measuring area was reduced as some trajectories exited the radar volume scan. In the downwind side areas near the edge of the radar measuring area experience improved precipitation detection. The effect of trajectory-correction is most prominent in instant measurements and diminishes when accumulating over longer time periods. Furthermore, measurements of intensive and small scale precipitation patterns benefit most from wind drift correction. The contribution of wind drift on the uncertainty of estimated Ze (S) - relationship was studied by simulating the effect of different error sources to the uncertainty in the relationship coefficients a and b. The overall uncertainty was assumed to consist of systematic errors of both the radar and the gauge, as well as errors by turbulence at the gauge orifice and by wind drift of precipitation. The focus of the analysis is error associated with wind drift, which was determined by describing the spatial structure of the reflectivity field using spatial autocovariance (or variogram). This spatial structure was then used with calculated drift distances to estimate the variance in radar measurement produced by precipitation drift, relative to the other error sources. It was found that error by wind drift was of similar magnitude with error by turbulence at gauge orifice at all ranges from radar, with systematic errors of the instruments being a minor issue. The correction method presented in the study could be used in radar nowcasting products to improve the estimation of visibility and local precipitation intensities. The method however only considers pure snow, and for operational purposes some improvements are desirable, such as melting layer detection, VPR correction and taking solid state hydrometeor type into account, which would improve the estimation of vertical velocities of the hydrometeors.
  • Sointu, Iida (2014)
    Preliminary estimation of wind speed at the wind turbine hub height is critically important when planning new wind farms. Wind turbine power output is proportional to the cube of wind speed which means that even small uncertainties in wind speed estimation will greatly affect the estimated energy yield. Wind resource estimation is usually based on wind measurements using meteorological masts and SODAR (SOnic Detection And Ranging) instruments. Modern wind turbine hub height typically ranges from 100 to 140 meters. Wind speeds measured with a mast must often be extrapolated to turbine hub height, while SODAR measures a continuous wind profile up to approximately 200 meters height. The goal of this study is to assess the uncertainty of SODAR measurements and to analyse the vertical wind profile variability in Finnish conditions from a wind power perspective. Mast and SODAR data collected at 17 sites across Finland covering a total of 381 months of measurements was available for this study. Both the amount and type of equipment at the sites as well as temporal data coverage varied greatly among the sites. Both coastal and inland sites were represented. Mast and SODAR data were quality controlled using manual inspection. The main reason for this was to identify periods with anemometer freezing, which results in erroneous wind data. Quality controlled data was used to calculate various parameters utilized in the wind resource assessment such as annual wind speed, wind shear represented by the power law exponent (alpha), atmospheric stability category and turbulence intensity. SODAR uncertainty was studied using the difference of wind speed measured by co-located mast and SODAR in relation to wind speed, humidity, alpha and turbulence intensity. Wind profile variability was studied with emphasis on hub height wind speed extrapolation, particularly in terms of profile shape and wind speed magnitude. Based on the results, the most common stability categories are neutral and slightly stable, which are related to relatively strong wind shear. Wind profiles were found to vary significantly with season. Therefore wind speed extrapolation should not be performed based on seasonal data when aiming for statistical representativeness of the wind resource. As a result of this study a statistical method to account for the seasonality is presented. SODAR was observed to overestimate horizontal wind speed in rainfall as well as in high wind speed and weakly turbulent conditions. Due to these tendencies, conducting short SODAR measurement campaigns in which the afore-mentioned conditions prevail is not recommended. As winters have generally higher wind speeds in Finland, short wintertime SODAR campaigns are discouraged. A verification measurement period for mast-SODAR intercomparison ought to be carried out before using SODAR as a standalone instrument. This should be conducted close to a meteorological mast and the period should include as much meteorological variability as possible. This would ensure some level of certainty in SODAR measurements, especially in the absence of an acknowledged calibration standard.
  • Pim, Jonathan (2022)
    Wolfe’s Theorem states that there is an isometric isomorphism between the space of flat k-cochains and the flat differential k-forms in R^n . The flat forms are the space of essentially bounded differential forms with an essentially bounded weak exterior derivative. The flat cochains are the dual space of the flat chains which are geometric objects based on finite linear combinations of k-simplices. In this sense, Wolfe’s Theorem connects geometry and analysis. After proving Wolfe’s Theorem, we give two corollaries: that the isomorphism from Wolfe’s Theorem can be concretely approximated by convolution with smooth mollifiers, and a version of Stokes’ Theorem for flat chains. Our method for proving Wolfe’s Theorem involves isometrically embedding the flat chains, as well as a predual of the flat forms, into the space of flat currents. By way of some approximation theorems in the space of flat currents, the images of these two embeddings coincide. Thus, the flat chains are isomorphic to that predual. This isomorphism lifts to their dual spaces giving Wolfe’s Theorem.
  • Zhou, Ziye (2018)
    As a response to the big data era, the generation of databases has been changed from relational to multi-model. In order to manage different database models with a single back-end, multi-model databases have been developed. However, how to manage these multi-models in a more efficient way is the most fundamental and pressing issue in the research of multi-model database. This thesis introduces a new algorithm called Xjoin which achieves worst-case optimality for multi-model join. In this thesis, we also designed a basic and intuitive algorithm named Baseline. We have done several experiments on these two algorithms. Finally, the comprehensive experiments show the efficiency and effectiveness of XJoin algorithm on various datasets and multi-model queries.
  • Viljamaa, Iiris (2019)
    Säätutkia käytetään sadealueiden liikkeiden ja sateen voimakkuuden arvioimisen. Säätutkan toimintaperiaate perustuu sille, että sen lähettämä mikroaaltopulssi siroaa ilmakehässä olevista partikkeleista kuten vesipisaroista ympäristöönsä, jolloin pieni osa lähetetystä pulssista heijastuu takaisin kohti tutkaa. Tutka vastaanottaa palanneen pulssin ja arvioi sen perusteella sadealueita. Säätutkat ovat mittalaitteita, jotka vaativat toimiakseen säännöllistä huoltoa ja mittaustulosten validointia. Säätutkan kalibrointi on monessa mielessä haasteellista. Tutka on kaukokartoituslaite, jonka keräämä data kattaa alueen aina 250 km säteelle tutkasta. Se ei mittaa suoraan sademäärää, kuten sademittarit yleensä, vaan arvio sen välillisesti tutkaheijastuvuuden kautta. Tämän tutkimuksen tarkoitus on tarkastella uutta mahdollista kalibrointimenetelmää. Uusi menetelmä käyttäisi pienoissadetutkaa MRR-2 vertailukohtana. Myös MRR-2 mittaa tutkaheijastuvuustekijää, joten se voisi olla hyvä vertailupari säätutkalle. Tasaisen sateen otoksessa vuosien 2015-2018 kesäsateissa säätutkan WRM200 ja pienoissadetutkan MRR-2 vertailupisteihin sovitetun suoran yhtälö on 𝑍(𝑊𝑅𝑀200) = 0.83 𝑍(𝑀𝑅𝑅−2) + 2.01, jossa 𝑍(𝑊𝑅𝑀200) on säätutkan ja 𝑍(𝑀𝑅𝑅−2) on pienoissadetutkan mittaama tutkaheijastuvuustekijä. Tasaisessa sateessa otoksen RMS-virhe on 3,36 dB. Konvektiivisen sateen otoksessa vastaava yhtälö on 𝑍(𝑊𝑅𝑀200) = 0.77 𝑍(𝑀𝑅𝑅−2) + 3.70 ja RMS-virhe 5,36 dB. Tasaisessa sateessa verrattavuus on konvektiivisessa sateessa tehtyä vertailua parempi. Tutkimus sisältää pohdintaa tuloksiin vaikuttavista tekijöistä sekä pohdintaa MRR-2:n soveltuvuudesta vertailulaitteeksi säätutkan kalibrointiin. Tutkimuksen pohjalta vaikuttaa siltä, että vaikka vertailunasettelu pyritään tehdä mahdollisimman vakaaksi, ei virhetekijöitä voida sulkea pois. Näin ollen tämän kaltaisella asettelulla ei voida suorittaa tarkkaa säätutkan kalibrointia.
  • Ollikkala, Sami (2017)
    Tässä tutkielmassa käsitellään röntgenabsorptiospektrometrilaitteistoa sekä lähireuna-absorptiospektroskopia -menetelmää. Tässä työssä esitellään Helsingin yliopiston röntgenabsorptiospektrometri sekä keskitytään XANES-menetelmään (XANES, X-ray Absorption Near Edge Spectroscopy). Absorptiospektroskopian avulla saadaan tietoa tutkittavan atomin lähiympäristöstä ja paikallisesta elektronirakenteesta. Menetelmä on erittäin tärkeä energian varastointimateriaalien sekä katalyyttimateriaalien tutkimuksessa, koska datan avulla päästään käsiksi esimerkiksi hapetuslukuihin. Röntgenabsorptiospektroskopia (XAS, X-ray Absorption Spectroscopy) voidaan karkeasti jakaa lähireuna- (XANES, X-ray Absorption Near Edge Spectroscopy) ja laajennettuun absorptioreunan hienorakenteen spektroskopiaan (EXAFS, Extended X-ray Absorption Fine-Structure Spectroscopy). XAS-menetelmä on alkuainespesifinen sekä herkkä mittaamaan kemiallisten sidosten pituuksia. XANES mittaa tilatiheyttä ja soveltuu hapetuslukujen määrittämiseen erittäin hyvin. Tämän tutkielman aikana Helsingin yliopiston XAS-laitteistolla suoritettiin mittaukset usealle standardinäytteelle, jotka valmistettiin paikan päällä. Näytteiden valmistus ja mittaukset suoritettiin huolellisesti ja koejärjestely pidettiin mittausten välillä samana. Työn tuloksina saatiin absorptiospektrit standardinäytteille, jotka sisältivät siirtymämetalleihin kuuluvien koboltin ja mangaanin oksideja. Tulosten perusteella Helsingin yliopiston röntgenlaboratorion XAS-laitteistolla voidaan mitata absorptiospektrit erittäin tarkasti. Mitatut spektrit ovat lähes identtiset kirjallisuusreferenssien kanssa. Koboltin K-reuna mitattiin 7,7 keV:n ja mangaanin 6,5 keV:n ympärillä. Tuloksista voidaan selvästi nähdä energiasiirtymät standardinäytteiden spektrien välillä. Laitteiston monokromaattorikide on suurin osatekijä, joka määrää äärellisen energian erotuskyvyn, joka on arviolta 1,5 eV. Kobolttioksidinäytteiden mittaustuloksista voidaan myös havaita absorptioreunan siirtyminen kohti suurempaa energiaa, koboltin hapetusluvun kasvaessa. Tulosten avulla pystyttäisiin määrittämään koboltin hapetusluvut.
  • Nieminen, Heta-Elisa (2018)
    Lithium ion batteries (LIBs) are used as power sources in most of portable devices, electronic cars and many other applications today. As the industry demands for smaller devices, new focus has raised for nanostructured electrodes and all solid state batteries. LIBs are rechargeable batteries, which means that Li+-ions migrate between anode and cathode reversibly. For the battery to work, the electrodes need to be stable when Li+-ions are intercalated and removed from the structure. LiMn2O4 is a promising material for a cathode, because the three-dimensional manganese oxide network enables intercalation of additional lithium ions also beyond the 1:1 Li:Mn stoichiometry resulting in structures in the range of LixMn2O4, 0 ≤ x ≤ 2. The non-stoichiometric behavior improves the specific capacity of the battery compared to other possible lithium intercalation cathode materials like LiCoO2 and LiNiO2. Atomic layer deposition (ALD) is a gas phase thin film deposition technique where the precursors are led to react on the surface one by one. Because no chemical reaction is taking place in the gas phase, the film growth is highly controllable and the resulting films have excellent purity and high uniformity and conformity. ALD is superior thin film deposition technique even on top of 3D structures and when depositing ultra-thin films. This makes it excellent technique to deposit electrode materials for LIBs. X-ray absorption spectroscopy (XAS) measures the absorption of the material as a function of x-ray energy. With a tunable light source it is possible to study a selected electron core shell of a specific element. XAS gives then information on the electronic structure as well as the local crystal structure of the selected atom in the material. Therefore, XAS is an excellent technique for studying the intercalation and de-intercalation processes of LiMn2O4. The literature part of this thesis describes the synthesis of LiMn2O4 thin films and the behavior of the material as a working cathode in LIB. The focus is especially on XAS studies on LiMn2O4. The experimental part involves a study on ALD grown β-MnO2 and LixMn2O4, 0 ≤ x ≤ 1, thin films with XAS, X-ray diffraction (XRD), X-ray reflectivity (XRR), time-of-flight elastic recoil detection analysis (TOF-ERDA), residual stress measurements and X-ray photoelectron spectroscopy (XPS). The aim of the study was to define how and where Li+ -ions intercalate in the β-MnO2 structure. To clarify the intercalation process, K and L core shells of manganese and K core shell of oxygen were studied with XAS. Samples were prepared at 225 ˚C by using earlier known ALD processes. First β-MnO2 film was deposited and then lithium was added by pulsing LiOtBu and H2O alternately on to the β-MnO2 film. The films were annealed after the deposition, however the lithium intercalation was observed to start already during the LiOtBu – H2O pulsing sequence. For the lithium intercalation mechanism, it is proposed that in the beginning the Li+-ions penetrate only to the top part of the β-MnO2 film and a lithium deficient non-stoichiometric phase LixMn2O4, 0 < x < 0.5, is formed. When the lithium concentration exceeds x ≈ 0.5 in LixMn2O4, the phase changes from the tetragonal pyrolusite to the cubic spinel, which enables Li+-ions to migrate throughout the whole film. Annealing in air after deposition seemed to convert the phase completely to the pure cubic spinel LiMn2O4.
  • Salosensaari, Aaro (2018)
    The applied mathematical field of inverse problems studies how to recover an unknown function from a set of possibly incomplete and noisy observations. One example of practical, real-life inverse problem is X-ray tomography, where one wishes to recover the internal composition of an object by taking several X-ray projection images from different directions around the object. The tomographic inversion task is a severely ill-posed problem in Hadamard's sense if a limited amount of measurement data is available for the reconstruction. Two examples of limited data tomography are sparse tomography and limited angle tomography. In sparse tomography, tomographic projections are taken with a sparse angular sampling, either because one wishes to reduce the radiation exposure of the object or have a faster imaging process. In limited angle tomography, projections are available only from a limited angular range. The numerous algorithms that have been proposed for solving the tomographic problem with limited data are based on taking account a priori information about the object of interest. In this thesis we study two such algorithms, total variation minimization and discrete tomography. In the total variation minimization the prior assumption is that the total variation of the reconstructed image is small. In the discrete tomography, it is assumed that the target object consists of only discrete amount of different, internally homogeneous materials. Smooth Discrete Algebraic Reconstruction Technique or SDART is a modern method for discrete tomography. In this thesis we study the problem of recovering the size, shape and the location of small submillimeter-sized voids enclosed in the wall of a metal pipe section. Tomographic reconstructions were found with the total variation minimization and SDART algorithms and also with a combination of both methods, which we call SDART-TV. The study setup is inspired by the problems involved in the radiographic inspection of steel pipe girth welds. During the welding process, various defects may form in the weld seam and affect negatively the structural properties of the weld. In industrial applications it is important to discover if such defects are present in the weld. The X-ray detectors suited for the existing devices for the radiographic pipe weld inspection can be small compared to the pipe diameter, which results in a difficult limited angle imaging geometry. The geometry of pipes also provides another source of prior information for the algorithms, as the space inside the pipe is often known to contain only air or similar matter. The performance of the total variation and algorithms for discrete tomography in the setup described above was studied with both computational simulations and experiments with an aluminium pipe phantom. The results of the experiments suggest that X-ray tomography algorithms based on a priori information could be applicable for non-destructive testing of pipe welds.
  • Roppo, Roope (2023)
    X-ray emission spectroscopy (XES) is an elemental characteristic x-ray technique that is used in studying the electronic properties of varied materials. It is based on an x-ray emission process that occurs due to an absorption process. First an x-ray photon is shot at the sample and electron in the inner core absorbs this x-ray photon. The electron gets kicked out of its place, creating an empty electronic state called an electron hole. This leaves the atom to an excited state that then de-excites by emitting an elemental characteristic x-ray photon. One of the main aspects of x-ray emission spectroscopy is to study sensitivity of XES towards different emission lines in different chemical environments and then compare the results. X-ray emission spectroscopy is a relatively easy technique to perform because it does not require a long-range crystal order and experiments can be done in an atmospheric pressure and in room temperature. A series of measurements were performed with non-resonant XES to study chemical properties of different uranium oxides. The experiment was done at the SOLEIL Synchrotron Facility in France. Main goal of the experiment was to study the sensitivity of XES to different uranium L3-emission lines by measuring different uranium oxides with different uranium oxidation states and compare the shape of each emission spectrum. The results showed that there are no visible differences between different samples when using non-resonant XES. However, the experiment also showed that when the resonant part is included in the measurements, then there are visible differences between different samples. This indicates the resonant part is required to collect to see differences in the spectrum when comparing the speciation of different samples.
  • Leino, Vesa-Matti (2020)
    A series of x-ray microtomography (micro-CT) measurements was performed on a set of rabbit femur bone samples containing artificial scaffolds of bioactive glass BAG-S53P4, implanted into an intentionally induced defect, i.e. a gap, in the femur. The scaffolds, some additionally enveloped in PLGA, were supportive structures composed of small granules of bioactive glass, intended to enhance, stimulate and guide the healing and regeneration of bone. The 34 samples were harvested from the rabbits at three different stages of healing and bone regeneration: 2 weeks, 4 weeks and 8 weeks. In addition to 27 samples that contained scaffolds of BAG-S53P4 or BAG-S53P4-PLGA, which had been implanted into the femur of a rabbit, 3 scaffolds of BAG-S53P4(-PLGA) that were not implanted and 7 control samples containing inert PMMA-implants were also included in the measurements for comparison. During the healing process the bioactive glass granules are gradually dissolved into the surrounding bodily fluids and a thin reaction layer composed of silica gel forms onto the surfaces of the granules. Subsequently an additional surface layer composed of HCA, a material that closely resembles natural hydroxyapatite, is formed onto the granules. As the healing process to regenerate the bone in the gap progresses, a complex three-dimensional network of newly formed trabecular bone grows in between the granules, attaching onto the surface layers and eventually enveloping the gradually dissolving granules entirely. Ultimately, the scaffold is intended to degrade completely, and a structure of regenerated, remodeled cortical bone is expected to be formed into the volume of the initial defect. As the thicknesses of both the surface layers of the granules and the individual trabeculae of the newly formed bone are in the micrometre range, x-ray microtomography was employed to evaluate and assess the complex three-dimensional structure, consisting of trabecular bone intertwined with granules at varying stages of dissolution. By evaluating the rate of formation of these structures at three different stages, i.e. time points, of regeneration, valuable information on the effectiveness of the bioactive glass BAG-S53P4(-PLGA) for the regeneration of defected bone can be obtained. The measurements were performed at University of Helsinki’s Laboratory of Microtomography using its Nanotom-apparatus with 80kV voltage, 150microA current and a voxel size of 15micrometres. 1000 projection images per sample were used in 37 reconstructions utilizing the FBP-algorithm. Subsequent image processing to analyze and compare the samples was conducted using ImageJ. A procedure to reduce image artefacts – due to metal parts in the samples – was developed, utilizing Gaussian filtering, as well as a preliminary image segmentation scheme, utilizing Morphological filtering, to automatically separate the bone from the granules and their surface layers.
  • Mattinen, Miika (2016)
    Ohutkalvojen mikrorakenne, joka käsittää esimerkiksi raekoon, tekstuurin ja jännitykset, vaikuttaa ohutkalvojen ominaisuuksiin ja edelleen kalvojen toimivuuteen erilaisissa sovelluksissa. Mikrorakenteen kehityksen ymmärtäminen on siten välttämätöntä kalvojen ominaisuuksien muokkaamiseksi eri sovellusten tarpeisiin. Ohutkalvojen mikrorakenteen kehitys alkaa ydintymisestä eli ensimmäisten kalvomateriaalin ydinten muodostumisesta substraatille. Ydintymisen jälkeen mikrorakenne kehittyy edelleen ydinten kasvu-, yhteensulautumis-, ja kalvon paksuuntumisvaiheiden aikana. Useissa sovelluksissa käytettävien ohutkalvojen paksuudet ovat viime vuosikymmeninä pienentyneet samalla, kun vaatimukset kalvojen luotettavuutta ja ominaisuuksia kohtaan ovat kasvaneet. Tämän vuoksi erityisesti ydintymisvaiheen tutkiminen, ymmärtäminen ja muokkaaminen on ensiarvoisen tärkeää. Kirjallisuusosiossa tarkastellaan mikrorakenteen kehittymisen yleispiirteitä sekä erityisesti ydintymistä ja mikrorakenteen kehitystä atomikerroskasvatuksessa (ALD). ALD-kalvojen ydintymisen ja erilaisten ydintymismallien lisäksi käsitellään aluksi amorfisena kasvavien ALD-kalvojen kiteytymistä kasvatuksen aikana sekä monikiteisten ALD-kalvojen mikrorakenteen kehittymistä paksuuntumisvaiheessa. Yleisluontoisempien havaintojen lisäksi mikrorakenteen kehitystä tarkastellaan yksityiskohtaisesti oksidien (erityisesti alumiinioksidi ja ryhmän 4 oksidit), platinametallien (Ru, Pt, Ir ja Pd) sekä kalkogenidien (erityisesti sinkkisulfidi) osalta ydintymisvaiheeseen keskittyen. Kokeellisessa osiossa tutkittiin Ir- ja IrO2-kalvojen atomikerroskasvatusta. ALD-platinametallikalvojen ydintymisvaihe ymmärretään lukuisista tutkimuksista huolimatta huonosti. Iridium on jäänyt sen hyvistä ominaisuuksistaan huolimatta enemmän tutkittujen platinan ja ruteenin varjoon sekä kalvojen ominaisuuksia että ydintymistä tutkittaessa. Tämän tutkielman kokeellinen osa on jaettu neljään osaan, joissa tarkastellaan iridiumin ja iridiumoksidin (IrO2) kasvatusta Ir(acac)3 (acac = asetyyliasetonaatti) -lähtöaineesta. Aiemmin tutkittujen Ir(acac)3+ilma-, Ir(acac)3+O2- ja Ir(acac)3+O3+H2-prosessien lisäksi iridiumia kasvatettiin uudella Ir(acac)3+O2+H2-prosessilla, jossa pinnalle adsorboitunut happi poistettiin vedyllä. Iridiumoksidia kasvatettiin aiemmin tutkitulla Ir(acac)3+O3-prosessilla. Ensimmäisessä osassa vertailtiin Ir- ja IrO2-prosessien ydintymisvaihetta. Ydintymisen havaittiin olevan nopeinta uudessa Ir(acac)3+O2+H2-prosessissa ja hitainta otsoniprosesseissa. Toisessa osassa uutta O2+H2-prosessia verrattiin eniten käytettyyn O2-prosessiin 200–350 °C lämpötila-alueella. Hapen poistaminen vaikutti selvästi kalvojen kasvunopeuteen, morfologiaan, karkeuteen, resistiivisyyteen, raekokoon ja tekstuuriin. Kolmannessa osassa tutkittiin Ir- ja IrO2-prosessien konformaalisuutta VTT:n kehittämien testinäytteiden avulla. O3+H2-prosessin konformaalisuus osoittautui tutkituista prosesseista selvästi parhaaksi. Tämän konformaalisuus oli erinomainen myös aiemmin kirjallisuudessa tutkittuihin ALD-platinametalliprosesseihin verrattuna. Viimeisessä luvussa tutkittiin otsonin mahdollista iridiumkalvoja etsaavaa vaikutusta. Etsautumista vaikutti tapahtuvan käytettäessä otsonia reaktanttina tai altistamalla kalvo otsonille jokaisen iridiumia kasvattavan ALD-syklin jälkeen. Aiemmin kasvatettujen iridiumkalvojen etsaaminen otsonilla ei kuitenkaan onnistunut.
  • Kaipiainen, Maria (2015)
    Yksi Loviisan ydinvoimalassa käytetyistä dekontaminointimenetelmistä on CORD-menetelmä. Dekontaminoinnin seurauksena syntyy jäteliuosta, jota käsitellään haihdutus- ja ioninvaihtomenetelmiä käyttäen. Käsittelyn jälkeen jäteliuoksen suolapitoisuus on korkea ja sen sisälttämien radioaktiivisten nuklidien, esimerkiksi 60Co:n, 63Ni:n, 54Mn:n ja 55Fe:n, erotusta varten tarvitaan tehokkaita puhdistusmenetelmiä. Nikkeli on yksi pitkäikäisistä radionuklideista, jotka ylläpitävät jätteiden korkeaa aktiivisuustasoa satoja vuosia jätteen syntyhetkestä lähtien. Nikkelin poisto jäteliuoksesta voisi pienentää huomattavasti loppusijoitettavan jätteen määrää. Tästä syystä nikkelin erotus on mielenkiintoinen tutkimusaihe. Fotokatalyysi on yksi mahdollisista menetelmistä, jota voidaan hyödyntää ydinjätteiden käsittelyssä. Fotokatalyysi on prosessi, jossa katalyytin ja ultraviolettisäteilyn avulla hajotetaan liuoksen sisältämät orgaaniset aineet yksinkertaisiksi ja haitattomiksi yhdisteiksi. Prosessissa käytetty katalyytti, useimmiten titaanidioksidi (TiO2), absorboi ultraviolettisäteilyä ja muodostaa hydroksyyli-radikaaleja, jotka ovat voimakkaita hapettimia. Orgaaniset aineet hajotetaan radikaalien avulla ja lopuksi nuklidit erotetaan ioninvaihdolla. Tämän pro gradu -työn tavoitteena oli kehittää nikkelin tehokas erotusmenetelmä Loviisan ydinvoimalan haihdutinjäteliuoksesta. Työn tarkoituksena oli testata erilaisia sorbentti-materiaaleja ja löytää niistä selektiivisin ioninvaihdin nikkelille. Työssä keskityttiin tinaoksidipohjaisiin materiaaleihin ja tutkittiin niiden sorptio- sekä fotokatalyyttiset ominaisuudet natriumnitraattiliuoksessa ja Loviisan haihdutinjäteliuoksen simulanttiliuoksessa. Puhtaan tinaoksidin ja fotokatalyyttisen hapetuksen yhdistelmällä saavutettiin lähes 100 %:nen nikkelin erotus yksinkertaistetusta natriumnitraattiliuoksesta. Menetelmän tehokkuus laski, kun liuoksen koostumus vaihtui monimutkaisemmaksi. Työssä todettiin, että tutkittu puhdas tinaoksidi on tehokkaampi sorbentti kuin kaupallinen Degussa-titaanioksidi yksinkertaisessa natrium-nitraattiliuoksessa. Tutkitun tinaoksidimateriaalin kolloidista liukenemista todettiin pH:n ollessa yli 8, mikä rajoittaa materiaalin käyttöä. Koeliuoksen pH vaikutti myös fotokatalyysiprosessin tehokkuuteen. Emäksisessä pH:ssa tinaoksidien fotokatalyyttinen tehokkuus nikkelin erotuksessa oli korkeampi kuin neutraalissa pH:ssa simulanttiliuoksessa. Lisäksi työssä todettiin, että oksalaatin läsnäolo koeliuoksessa häiritsi nikkelin sorptiota sorbentin pinnalle natriumnitraattiliuoksessa, mutta ei simulanttiliuoksessa. Koeliuoksen oksalaattipitoisuuden nostaminen laski fotokatalyysin tehokkuutta. Nikkelin fotokatalyyttinen erotus oksalaattia sisältävässä liuoksessa vaati pitkää säteilytysaikaa, mikä ei ole suotavaa ydinvoimalan jäteliuosten käsittelyssä.
  • Vasara, Leena (2019)
    Suuri määrä ydinvoimaloita on tulossa lähivuosina ja -vuosikymmeninä käytöstäpoisto vaiheeseen. Valtavasta käytöstäpoisto- ja purkamistöistä syntyy tuhansia tonneja jätettä. Osa tästä jätteestä on metallijätettä, joka voidaan kierrättää ja käyttää uudelleen dekontaminoinnin jälkeen. Kirjallisuusosassa tarkastellaan erilaisia dekontaminaatiomenetelmiä sekä dekontaminoimisessa syntyvän happaman sekundäärisen liuosjätteen käsittelyä ioninvaihtimilla. Pääpaino on primääripiirien kemialliseen dekontaminaatioon soveltuvissa menetelmissä. Näistä CORD (Chemical Oxidation Reduction Decontamination) on yksi käytetyimmistä maailmalla. Tutkimuksen tavoitteena oli löytää ioninvaihtomateriaaleja, jotka pystyisivät tehokkaasti ottamaan Co-60:a ja Ni-63:a CORD tyyppisistä dekontaminaatioliuoksista. Co-60 ja Ni-63 esiintyvät yleisesti primääripiirien korroosiokerroksissa. Co-60 usein määrittää käytössä olevan ydinvoimalan säteilytason ja Ni-63:stä tulee merkittävin säteilyn aiheuttaja 20 vuotta reaktorin sulkemisen jälkeen. Kokeellisessa osassa tutkittiin seitsemän epäorgaanisen ioninvaihtomateriaalin kykyä ottaa Co-60:a ja Ni-63:a CORD -tyyppisistä dekontaminaatioliuoksista. Tutkimuksissa selvitettiin materiaalien kemiallista kestävyyttä ravistelemalla ioninvaihtimia oksaali- ja permanganaattihapoissa kahden viikon ajan. Liuoksista mitattiin metallipitoisuus MP-AES:lla tai ICP-MS:llä. Lisäksi selvitettiin materiaalien ioninvaihtokyky nuklidien suhteen eri pH -arvoissa. Ioninvaihtokyvyn mittana käytettiin jakaantumiskerrointa. Näiden alkumittausten jälkeen jatkoon valittiin kolme materiaalia, joiden ioninvaihtokykyä testattiin happamissa oloissa oksaalihapossa ja kaliumpermanganaatissa. Lisäksi selvitettiin ioninvaihtimien tehoa, kun läsnä on myös kilpailevia ioneja (Fe, Cr, Ni /Co). Kd -arvot määritettiin mittaamalla Co-60 liuokset Wizardin gammalaskurilla ja Ni-63 liuokset Perkin Elmerin nestetuikelaitteella. Osa ioninvaihtimista ei toiminut juuri lainkaan happamissa oloissa eikä niiden tutkimista kannattanut jatkaa alkutestien jälkeen. Tutkimuksissa löytyi kolme hyvin tai kohtuullisesti happamissa oloissa toimivaa ioninvaihdinta: Sb2O5, CoTreat ja MnO2. Kd -arvot olivat pääasiassa parempia Co-60 kuin Ni-63 suhteen kaikissa testeissä. Sb2O5:lla saavutettiin pH:ssa 2 jopa Kd arvo 25 000 (Co-60) mutta arvo puolittui, kun mukana oli oksaalihappoa. Ni-63 suhteen Kd oli enää 100 – 1000 välillä oksaalihapossa. Mitatut tulokset vaihtelivat paljon eri kokeissa.