This study investigates the differences and similarities in implementation of anti-doping policy in Denmark and Iceland. Various anti-doping themes has been chosen to dig deeper into the implementation on policies between the two countries which are related to: Economy, Education, Testing and Investigation, International Cooperation, Fitness and Public Health and Research and Development.  A comparison of the implementation is done where governance and power within anti-doping is analyzed in the countries. The aim is to outline the ways the two countries implement anti-doping policy, analyze how their NADOs are governed as well as how power and interconnections are divided between the stakeholders of anti-doping. Document analysis and a semi structured interview was conducted in order to collect the data needed for the investigation and analysis process. A thematic analysis was developed to be able to gather the most vital and reliable data on the selected anti-doping themes. Additionally, theory on power, interconnections and good governance was implemented to reach towards the purpose of this study. The analysis showed different outcomes in the two countries. Denmark implements the international anti-doping policy to a high degree where they adapt to it in relation to national strategies in sport. Iceland has difficulties in adapting to every anti-doping standard of the international policy and focuses on the ones of most importance to Icelandic sport and society.  The study concluded that both countries implement and comply to the international anti-doping policy by law and have independent NADOs that are responsible for anti-doping nationally. Despite complying to the international law, the implementation differs in the countries which is affected by national prioritization and resources. The main focus of Iceland is education and testing where Denmark is more developed within their NADO and prioritizes every standard to a certain degree. The NADOs are steered by the policies set by WADA and their governments who are running political and corporate governance. Furthermore, the study concluded that the interconnected relationship between the stakeholders of anti-doping is complex and there are often difficulties between the NADOs, the ministries and/or WADA which also involves the power relationship between the stakeholders.

Doping has serious negative consequences for athletes and the integrity of sports, implying the need for effective prevention programs. Since educating young athletes about doping-related knowledge is deemed to be not sufficiently effective to minimize doping, a focus on values, emotions and morality is seen as a promising approach and previous research indicates which variables exactly could be addressed in anti-doping efforts. These variables are anticipated guilt, empathy, moral disengagement, and collective moral norms, since these constructs have been strongly and consistently linked to doping intention, likelihood, or behavior. Therefore, the purpose of this study was to develop a values-based anti-doping intervention, which targets the aforementioned variables, and to evaluate its effectiveness in producing changes in outcomes in comparison to an information-based intervention and a waiting control group. To evaluate their effectiveness, both interventions, which each consist of six 45-min sessions (one session per week) were implemented in a sample of 321 young elite athletes, aged 13–19 years, from a broad range of team and individual sports. Thirty different teams, training groups or classes were randomly assigned to either the values-based intervention, the information-based intervention, or to a waiting control group. Doping intention, doping susceptibility as well as the above mentioned variables were assessed at pre- and posttest and, for participants of the values- and information-based conditions also at a 3 to 4-month follow up. Within a multilevel modeling framework general linear mixed regression analyses revealed that the values-based intervention, compared to the control group, was able to decrease athletes' moral disengagement and increase their anticipated guilt immediately after the intervention (at posttest), whereas no effects for the information-based intervention emerged. Looking at how the outcomes developed over time (i.e., at the follow up measurement), it could be demonstrated that the reduction in moral disengagement sustained. The increase in anticipated guilt, however, was not sustainable and, surprisingly, decreased from post to follow up. Furthermore, athletes in the values-based intervention reported higher empathy from post to follow up, which could possibly indicate a “delayed” effect. This study provides support that a values-based approach can produce changes in some, yet, not all addressed variables and specific elements from this intervention could potentially be a useful addition to traditional anti-doping education (i.e., information provision).

The topic of this thesis is the study of nitrogen functionalities in nitrogen-doped reduced graphene oxide using Raman spectroscopy. Specifically, the project set out to investigate if the Raman active nitrogen-related vibrational modes of graphene can be identified via isotope labelling. Previous studies have used Raman spectroscopy to characterise nitrogen doped graphene, but none has employed the method of isotope labelling to do so. The study was conducted by producing undoped, nitrogen-doped and nitrogen-15-doped reduced graphene oxide and comparing the differences in the first-order Raman spectrum of the samples. Results of this study are inconclusive. However, some indications linking the I band to nitrogen functionalities are found. Also, a hypothetical Raman band denoted I* possibly related to \spt{3} hybridised carbon is introduced in the same spectral area as I. This indication of a separation of the I band into two bands, each dependent on one of these factors could bring clarity to this poorly understood spectral area. As the results of this study are highly speculative, further research is needed to confirm them and the work presented here serves as a preliminary investigation.

Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Douglas S. McGregor / Strengthening the crystal lattice of lanthanide halides, which are brittle, anisotropic, ionic crystals may increase the availability and ruggedness of these scintillators for room-temperature γ-ray spectroscopy applications. Eight dopants for CeBr[subscript]3, including CaBr[subscript]2, SrBr[subscript]2, BaBr[subscript]2, ZrBr[subscript]4, HfBr[subscript]4, ZnBr[subscript]2, CdBr[subscript]2, and PbBr[subscript]2, were explored at two different doping levels, 500ppm and 1000ppm, in an effort to identify potential aliovalent strengthening agents which do not adversely affect scintillation performance. All dopants and doping levels exhibited improved ingot yields over the undoped case, indicating an improvement in the ease of crystal growth. Scintillation performance was gauged using four key metrics. Scintillation emission spectra or, rather, radioluminescence spectra were recorded using x-ray irradiation. Total light yield was estimated through pulse height comparison with bismuth germanate (BGO) scintillators. Scintillation kinetics were checked by measuring single interaction pulses directly output by a fast response PMT. Finally, light yield proportionality was measured using a Compton coincidence system. Samples from each ingot were harvested to benchmark their performance with the four metrics. Of the eight dopants explored, only BaBr[subscript]2 and PbBr[subscript]2 clearly altered scintillation spectral emission characteristics significantly. The remaining dopants, CaBr[subscript]2, SrBr[subscript]2, ZrBr[subscript]4, HfBr[subscript]4, CdBr[subscript]2 and ZnBr[subscript]2, altered scintillation performance to a lesser degree. No dopant appeared to affect light yield proportionality, nor did any drastically alter the light decay characteristics of CeBr[subscript]3. HfBr[subscript]4 and ZnBr[subscript]2-doped CeBr[subscript]3 exhibited the highest light yields, significantly higher than the undoped CeBr[subscript]3 samples tested. Finally, aliovalent doping appeared to greatly improve CeBr[subscript]3 ingot yields, regardless of the dopant, thus it is a promising method for improving crystal strength while not deleteriously affecting scintillation performance. HfBr[subscript]4 and ZnBr[subscript]2 both demonstrated high performance without any noticeable negative side-effects and are prime candidates for future study.

<p>Over the past decade, the study of zinc oxide (ZnO) II-VI semiconducting nanostructures has been a burgeoning research area because of this material's unique electrical and optical properties. Despite the promise of its characteristics for numerous applications, usage of ZnO in the fabrication of nanoscale devices on a commercial scale remains a challenge because of our lack of knowledge of the underlying physics and chemistry of nanostructures. Sustainable progress in nanowire manufacturing techniques requires that we first undertake basic studies to address these poorly understood underlying concepts before we embark on applied engineering. If these fundamental studies prove successful, then characterization, fabrication, and large-scale integration of nanostructures that use ZnO could be applied to a range of engineering fields. This doctoral dissertation is primarily concerned with the synthesis and doping required for the creation of novel ZnO nanostructures and the growth mechanisms of such structures. Numerous studies have been made of various kinds of ZnO nanostructures. However, no studies have been reported of systematic theoretical modeling that uses both density functional theory and as-synthesized nanostructures to explain the growth mechanisms involved in these devices. First, sulfur-doped ZnO nanostars, synthesized through a hydrothermal method, will be discussed. This section uses ab initio simulations in discussing the synthesis of novel ZnO nanostructures and their proposed growth mechanisms. Moreover, this discussion also addresses the optical properties of ZnO structures that cause sulfur doping to enhance their emission of green light. The next section introduces a novel synthetic methodology to reliably produce well-aligned vertical ZnO nanowire arrays on amorphous substrates. Vertical alignment of nanowires significantly improves the performance of devices like LEDs and solar cells. Because these vertically aligned arrays have historically been made using sapphire substrates that hinder their commercialization, substantial effort has been invested in using ZnO nanocrystal seeds to grow vertically aligned ZnO nanowires on silicon substrates. Well-known synthetic methods, such as zinc acetate dissolved in methanol or zinc acetate combined with sodium hydroxide (or potassium hydroxide), have typically been used in pursuit of this goal without a detailed understanding of the mechanisms of seed creation. The consequence of this lack of knowledge has been inconsistent reproducibility in growing vertically aligned nanowires on silicon substrates. This discussion includes the details of mechanisms that explain the why and how of creation of vertical/misoriented ZnO nanocrystal seeds on silicon substrates. In addition, a preferential c-axis-oriented ZnO nanocrystal seed has been successfully synthesized using a solution composed of ammonium hydroxide (NH4OH) and zinc acetate (Zn(O2CCH3)2). Lastly, the synthesis of sea urchin-like microstructures known as ZnO sea urchins will be introduced. Among the various kinds ZnO structures, the ZnO sea urchin is a integrated structure composed of a 3-D microsphere and 1-D nanowires. Dye-sensitized solar cells (DSSCs) made of ZnO sea urchins have shown a higher power conversion efficiency than planar nanowires. This is because ZnO sea urchins have a higher surface area per unit of volume than planar nanowire arrays. This larger surface area allows larger amounts of dye to access the semiconducting nanowires. We have synthesized the sea urchin structures composed of ZnOxPy microspheres, a mixed of zinc phosphide (Zn3P2) and ZnO phase, encapsulated in an array of ZnO nanowires. Synthesis of these interesting structures was achieved without resorting to the prefabricated 3-D microsphere templates that other groups used in previous studies. This new approach to the synthesis of ZnO sea urchin structures was accomplished by simply adding Zn3P2 powder to the C (graphite) and ZnO source powders in a chemical vapor transport method. The ZnO sea urchin's material properties and growth mechanism will be characterized and discussed in detail.</p> / Dissertation

This thesis focuses on understanding the chemistry involved in a variety of surface modification reactions, both on metal oxides and graphene. In this work, the rates of chemisorption of a prototypical phosphonic acid on ITO under several processing protocols are measured using XPS to determine the optimal procedure. UPS is used to track the dependence of the electronic structure of the system, specifically of the work function and position of the valence band maximum on coverage. Phosphonic acid monolayers with appropriate tail groups can also be used to initiate chemistry from surfaces, which has potential for building layers of organic-electronic devices, including organic solar cells and capacitors. The growth of non-conjugated polymers from BaTiO₃ nanoparticles using a facile ATRP technique is studied via solution-phase and solid-state techniques to determine its applicability to make matrix-free composites for hybrid dielectrics. In addition, the surface chemistry involved in Kumada Catalyst-Transfer to grow polythiophene derivatives from ITO is examined via XPS. Finally, the newly emerged alternative for replacement of ITO as transparent electrode, graphene, is n- and p-doped using redox-active, solution-processable metal-organics, which increased its conductivity and allowed the work function to be tuned over a range of 1.8 eV. The systems are characterized in a systematic study, and the results are promising for future applications of graphene.

Electrical doping of organic semiconductors with molecular oxidants (p-type) or reductants (n-type) can greatly improve charge injection and conductivity in devices. Simple one electron reductants that are capable of reducing most electron-transport materials will inevitably also be sensitive to reaction with oxygen. Coupling electron transfer step with bond breaking/ making processes in principle can address this problem. The rhodocene dimer and related ruthenium and iridium dimeric sandwich compounds have been discussed as example of such n-dopants, reducing a variety of organic semiconductors to the corresponding radical anions, while forming monomeric cations. This class of n-dopants can be used in both vapor- and solution-processed devices, and the dopant monomer cations are large and, therefore, fairly stable with respect to diffusion. This thesis focused on increasing the utility of these and related electrical dopants. In order to reduce various electron-transport materials with lower electron affinities, which are frequently used in OLEDs, strategies and limitations to develop stronger n-dopants is discussed. Controlling the kinetics of the dopant / semiconductor reactions to allow film processing in ambient conditions, with activation of the dopants being carried out thermally or photochemically in subsequent steps is presented. An approach to covalently tether monomeric cations with themselves, surfaces or electron-transport materials is described. Electrochemical studies that further our understanding of dopant kinetics and thermodynamics is described. The dimer dopant chemistry is also compared to the corresponding hydride-reduced complexes of the cations and manganese tricarbonyl benzene dimer. The directions for future dopant design with improved properties is discussed.

The aim of this thesis is to examine the extent to which selected aspects of sport policy in Japan and also UK/England are influenced by international forces. The objectives which underpin the research aim are to analyse the characteristics of the domestic policy areas and identify the varying degree of impact of external influences on domestic sport policy. The thesis examines the interactions between domestic and international factors that shape elite sport policy and anti-doping policy and seeks to identify how domestic institutional values and ideas have been shaped by global influences. Importantly, by analysing the nature and mechanisms of global influence that are manifest at the domestic level, it is intended to identify varying degree of impact external to national policy. To achieve the above objectives, a qualitative methodology and related documentary research methods are adopted in the empirical investigations. Policy document analysis and semi-structured interviews are employed. The cases of UK (or England where appropriate) are introduced in order to generate a deeper understanding of the development of Japanese elite sport and anti-doping policy. The thesis draws on a range of theoretical frameworks, including international relations theory, international regime theory and globalisation, to analyse the empirical data. By adopting these theoretical frameworks, it is aimed to identify the possible characteristics of international policy regimes in the policy areas of elite sport and anti-doping.

Formaldehyde is a ubiquitous and hazardous indoor air pollutant and reducing concentrations in indoor environments is a public health priority. The goals of this doctoral work were to advance analytical methods for continuous monitoring of formaldehyde at very low concentrations (sub-20 ppb[subscript v]) and to improve fundamental, mechanistic understanding of how structural and chemical properties of activated carbon influence removal of formaldehyde from indoor environments. To achieve these goals, emerging sensor-based technology was evaluated for its ability to detect and quantify ppb[subscript v]-level formaldehyde concentrations on a continuous basis at relative humidity levels characteristic of residential indoor environments. Also, a combination of spectroscopic and selective titration techniques was employed to characterize molecular-level structural and chemical properties of traditional and chemically treated granular activated carbon (GAC). In addition to selecting two different commercially available GACs for study, design and preparation of a laboratory-prepared, chemically treated GAC was pursued to create nitrogen-doped GAC with desirable surface chemical properties. Performance of all GACs was evaluated with respect to formaldehyde removal through a series of packed bed column studies. With respect to continuous formaldehyde monitoring, a method detection limit for emerging sensor technology was determined to be approximately 2 ppb[subscript v], and for relative humidity levels characteristic of indoor environments (> 40%), quantitative, continuous formaldehyde measurements less than 10 ppb[subscript v] were robust. The two commercially available GACs tested were both capable of removing formaldehyde; however, the GAC with greater density of basic surface functional groups and greater electron-donating potential (Centaur) removed twice as much formaldehyde (on a GAC mass basis) as the less basic GAC (BPL). A laboratory-prepared GAC (BPL-N) was successfully created to contain pyridinic and pyrrolic nitrogen, which was associated with increased surface density of basic functional groups, as well as with increased electron-donating potential. BPL-N exhibited better removal capacity for formaldehyde than BPL and Centaur. Furthermore, packed bed column studies of BPL-N and BPL formaldehyde removal performance yielded evidence to support the hypothesis that electron-donating potential, especially nitrogen functional groups at the BPL-N surface, promote catalytic removal of gas-phase formaldehyde via oxidation. / text

Chalcogenide glasses and glass-ceramics present a high interest for the production of thermal imaging lenses transparent in the 3-5 μm and 8-12 μm windows. However, chalcogenide glasses are conventionally synthesized in sealed silica ampoules which have two major drawbacks. First, the low thermal conductivity of silica limits the sample dimensions and second the silica tubes employed are single use and expensive, and represent up to 30% of the final cost of the material. The present work therefore addresses the development of innovative synthesis methods for chalcogenide glass and glass-ceramics that can present an alternative to the silica tube route. The method investigated involves melting the raw starting elements in reusable silica containers. This method is suitable for the synthesis of stable chalcogenide glasses compositions such as GeSe₄ but uncontrolled crystallization and homogenization problems are experienced for less stable compositions. The second approach involves preparation of amorphous chalcogenide powders by ball milling of raw elements. This mechanosynthesis step is followed by consolidation of the resulting powders to produce bulk glasses. Hot Uniaxial Pressing is suitable for compositions stable against crystallization. However, uncontrolled crystallization occurs for the unstable 80GeSe₂-20Ga₂Se₃ glass composition. In contrast consolidation through Spark Plasma Sintering (SPS) allows production of bulk glasses in a short duration at relatively low temperatures and is appropriate for the synthesis of unstable glasses. A sintering stage of only 2 min at 390°C is shown to be sufficient to obtain infrared transparent 80GeSe₂-20Ga₂Se₃ bulk glasses. This method enables the production of lenses with a 4-fold increase in diameter in comparison to those obtained by melt/quenching technique. Moreover, increasing the SPS treatment duration yielded infrared transparent glass-ceramics with enhanced mechanical properties. This innovative synthesis method combining mechanosynthesis and SPS has been patented in the framework if this study. The controlled etching of 80GeSe₂-20Ga₂Se₃ glass-ceramics in acid solution yields nanoporous materials with enhanced surface area. The porous layer created on the surface of the glass-ceramic is shown to play the role of anti-reflection coating and increase the optical transmission in the infrared range by up to 10%. These materials may have potential for the production of sensors with increased sensitivity in the infrared. The influence of indium and lead addition on the thermal and optical properties of the 80GeSe₂-20Ga₂Se₃ glass has also been assessed. Increased In or Pb contents tend to decrease the Tg of the glasses and shift the optical band gap toward higher wavelengths. A systematic ceramization study emphasizes the difficulty of controlling the crystallization for glasses in the systems GeSe₂-Ga₂Se₃-In₂Se₃ and GeSe₂-Ga₂Se₃-PbSe. No crystallization of the In₂Se₃ and PbSe crystalline phase was obtained. Finally, the possibility of producing rare-earth doped 80GeSe₂-20Ga₂Se₃ glass-ceramics transparent in the infrared region up to 16 μm is demonstrated. Enhanced photoluminescence intensity and reduced radiative lifetimes are observed with increased crystallinity in these materials.