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Distributionsförluster är en viktig faktor i fjärrenergisystem. Genom att optimera förluster i sådana system, kan både ekonomiska och miljömässiga aspekter uppfyllas. Tyvärr finns det ringa information om rörförluster i fjärrkylasystem. Föreliggande studie fokuserar på förluster i ett fjärrkylanät genom att både använda ett R-nätverk och FEM simuleringsmodeller. Ett R-nätverksmodell bestående av termiska konduktanser har utvecklats genom analytiska ekvationer och simuleringar med FEM har utfört för validering av modellen. Därefter har ett fjärrkylanätverk som konstrueras i Gävle, analyserats. Undersökningen omfattar 15 olika rördiametrar i tre utföranden (dubbelrör med två symmetriska och en osymmetrisk värmeisolering) och i tre förläggningsdjup (0,8; 2 och 4 meter) för en säsong om 7 månader (April t o m Oktober). Särskilt utreds ökningen av temperaturen hos framledningsmediet, där matningsrören förlagts i en å mitt i staden om en sträcka av 1 km. Den maximala förlusten under säsongen, bland alla rörkonfigurationer, motsvarar 2 % av den totala levererade energin. Slutligen konstateras att kombinationen av isolerad framledningsrör och oisolerade returrör verkar som en gångbar investering, ekonomiskt och tekniskt, men kan inte användas i hela nätet eftersom stora delar har redan byggts med oisolerade plaströr. R-nätverksmodellen, som visades vara effektiv och pålitlig i undersökningen, kan som beräkningsverktyg, framförallt för dimensionering och för att uppskatta energiförluster. / Distribution losses are a very important factor in district energy systems. By optimizing the losses in such a system, both economical and environmental aspects can be fulfilled. Unfortunately, there is few information regarding losses for district cooling systems. This study focuses on losses in district cooling networks by using both R-network and FEM simulation models. A R-network model composed of thermal conductances has been developed through analytical equations and simulations have been performed for validation. Afterwards, an in-progress construction project of a district cooling network from the city of Gävle, Sweden, is analyzed. The assessment consists of 15 pipe diameters in three configurations (two symmetric cases and one asymmetric), at three ground laying depths (0.8, 2 and 4 meters) for a duration of 7 months (April to October). A particular case in which the main distribution pipes from and to the plant are submerged in the city’s river for a distance of 1 km is investigated in order to estimate the temperature increase of the supply water. A maximum cooling loss below 2% of the total delivered energy during the season for any network configuration resulted from the calculation. Finally, the mixed pipes array seems to be a feasible investment both economically and technically but it cannot be used for the entire network spread since a part of the network has been already built with the non-insulated plastic pipes. The R-network model proved to be effective and reliable in the analysis which provides confidence that it can serve as a solid foundation for a calculation tool - primarily for design purposes and also for estimating energy loss.

abstract: In-situ environmental transmission electron microscopy (ETEM) is a powerful tool for following the evolution of supported metal nanoparticles under different reacting gas conditions at elevated temperatures. The ability to observe the events in real time under reacting gas conditions can provide significant information on the fundamental processes taking place in catalytic materials, from which the performance of the catalyst can be understood. The first part of this dissertation presents the application of in-situ ETEM studies in developing structure-activity relationship in supported metal nanoparticles. In-situ ETEM studies on nanostructures in parallel with ex-situ reactor studies of conversions and selectivities were performed for partial oxidation of methane (POM) to syngas (CO+H2) on Ni/SiO2, Ru/SiO2 and NiRu/SiO2 catalysts. During POM, the gas composition varies along the catalyst bed with increasing temperature. It is important to consider these variations in gas composition in order to design experiments for in-situ ETEM. In-situ ETEM experiments were performed under three different reacting gas conditions. First in the presence of H2, this represents the state of the fresh catalyst for the catalytic reaction. Later in the presence of CH4 and O2 in 2:1 ratio, this is the composition of the reacting gases for the POM reaction and this composition acts as an oxidizing environment. Finally in the presence of CH4, this is the reducing gas. Oxidation and reduction behavior of Ni, Ru and NiRu nanoparticles were followed in an in-situ ETEM under reacting gas conditions and the observations were correlated with the performance of the catalyst for POM. The later part of the dissertation presents a technique for determining the gas compositional analysis inside the in-situ ETEM using electron energy-loss spectroscopy. Techniques were developed to identify the gas composition using both inner-shell and low-loss spectroscopy of EELS. Using EELS, an "operando TEM" technique was successfully developed for detecting the gas phase catalysis inside the ETEM. Overall this research demonstrates the importance of in-situ ETEM studies in understanding the structure-activity relationship in supported-metal catalysts for heterogeneous catalysis application. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2011

This thesis describes studies on two-dimensional electron gases (2DEG) in graphene and related 2D systems. Magnetotransport investigations specifically in graphene and its bilayer system are demonstrated in detail, while the experimental techniques presented in this thesis are widely applicable to a large variety of other 2D materials. Chapter 1 gives an introduction and motivation for the principal topic presented in this thesis, with a general introduction to carbon nano-materials and an overview of the current state of graphene-related research and technological development (RTD). Chapter 2 establishes a basic theoretical framework which is essential for interpreting the results presented in this thesis, starting with the crystal and electronic band structures of graphene and its bilayer, followed by high magnetic fields effects on transport properties in these 2D systems. Chapter 3 details the experimental methods directly related to the presented work. The next three chapters report experimental results of three specific magnetotransport studies. Chapter 4 reports the disorder effects on epitaxial graphene in the vicinity of the Dirac point. Quadratic increases of carrier densities with temperature are found to be due to intrinsic thermal excitation combined with electron-hole puddles induced by charged impurities. It is also shown that the minimum conductivity increases with increasing disorder strength, in good agreement with quantum-mechanical numerical calculations. Chapter 5 reports measurements of the quantum Hall effect in epitaxial graphene showing the widest quantum Hall plateau observed to date extending over 50 T, attributed to a magnetic field dependent charge transfer process from charge reservoirs with exceptionally high densities of states in close proximity to the graphene. Using a realistic framework of broadened Landau levels this process is modelled in excellent agreement with experimental results. In Chapter 6, energy relaxation of hot carriers in graphene bilayer systems is investigated from measurements on Shubnikovde Haas oscillations and weak localisation. The hot-electron energy loss rate follows the predicted T⁴ power-law at carrier temperatures from 1.4 up to about 100 K, due to electron-acoustic phonon interactions. Comparisons are made between graphene monolayer and bilayer systems and a much stronger carrier density dependence of the energy loss rate is found in the bilayer system. This thesis concludes with a summary of the most important findings of the topics that have been discussed. The significance and limitations of the present research are listed. Some suggestions and outlook are given for possible improvements and interesting areas of future research and development.

En raison de leur faible consommation d'énergie, les mémoires non volatiles (MNV) sont En raison de leur faible consommation d'énergie, les mémoires non-volatiles sont particulièrement intéressantes pour l'électronique portative (clé USB, téléphone, ordinateur portable …). Les mémoires Flash, qui dominent le marché, atteignent leurs limites physiques et doivent être remplacées. L'introduction de nouveaux matériaux et architectures mémoire est proposée. Les mémoires OxRRAM (Oxide Resistive Random Access Memory) sont des candidats potentiels. Il s'agit de structures M-O-M (Métal-Oxyde-Métal). Le stockage de l'information est basé sur la modulation de la résistance de l'oxyde à l'application d'un champ électrique ou d'un courant. Une meilleure compréhension du mécanisme de changement de résistance de ces dispositifs est nécessaire pour contrôler leurs performances. Nous nous intéressons au claquage diélectrique de l'oxyde, qui initie le mécanisme de changement de résistance. Les mesures physico-chimiques à l'échelle nanométrique sont indispensables à sa compréhension et font défaut dans la littérature. Dans cette thèse, nous proposons des mesures physico-chimiques, des mesures électriques et des méthodes de préparation d'échantillon adaptées. Les oxydes de nickel et d'hafnium sont investigués. En plus de la dégradation électrique (chute de résistance), les modifications de ces deux oxydes sont investiguées à trois niveaux : la composition chimique, la morphologie et la structure électronique. Mots-clés : mémoire résistive, mécanisme de changement de résistance, claquage diélectrique, NiO, HfO2, spectroscopie de photoélectrons, microscopie électronique en transmission, microscopie à forme atomique, lacunes d'oxygène. / With low energy consumption, non-volatile memories are interesting for portative applications (USB, mobile phone, laptop …). The Flash memory technology is reaching its physical boundaries and needs to be replaced. New materials and architectures are currently investigated. Oxide Resistive Random Access Memory (OxRRAM) is considered as a good candidate. It is based on a M-O-M (Metal-Oxide-Metal) stack. The information is stored using an electric field or a current that modulates the resistance of the oxide. A better understanding of the resistance switching mechanism is required in order to control the performances of the devices. We investigate the dielectric breakdown that activates the resistance switching properties. Physico-chemical characterization at the nanoscale is required. In this work, we propose proper physico-chemical and electrical measurements. Sample preparation is also considered. Nickel and hafnium oxide are investigated. Besides the evolution of the electrical properties, we analyze the oxide modification at three levels : the chemical composition, the morphology and the electronic structure. Keywords : resistive memory, resistance switching mechanism, dielectric breakdown, NiO, HfO2, photoelectron spectroscopy, electronic transmission microscopy, atomic force microscopy, oxygen vacancies.

Les nombreuses applications du dioxyde de titane TiO2 sont depuis longtemps l’objet d’un intense effort de recherche. En particulier, TiO2 peut potentiellement jouer un rôle clé dans les industries vertes et les sources d’énergie renouvelables. Chimiquement inerte à l’état stœchiométrique, ses applications s’appuient principalement sur la forme réduite TiO2-x, dont les propriétés sont liées aux lacunes d’oxygène (Ovac) et aux atomes de titane interstitiels (Tiint) à travers lesquels le changement de stœchiométrie s’opère. La réduction de l’oxyde, qui transforme formellement Ti4+ en Ti3+, génère des électrons en excès qui, peuplant des états Ti 3d dans la bande interdite (BGS), sont au centre de l’activité chimique de TiO2 et à l’origine de sa conductivité de type n. Le présent travail a porté sur trois questions centrales qui restent pendantes à ce jour, le rôle respectif de Ovac et Tiint dans la formation des BGS, l’apparente contradiction entre la conductivité de type n de l’oxyde et le caractère de donneur profond des BGS et la nature du transport électronique dans l’oxyde. L’origine, la localisation et le transport des charges en excès ont été explorés dans le cas du rutile TiO2(110)-(1×1) par mesures HREELS (High Resolution Electron Energy Loss Spectroscopy) combinées à des simulations diélectriques. Des approches expérimentales et des traitements d’échantillon spécifiques ont été utilisés, dont (a) le chauffage de la surface entre 400 et 900 K par exposition à un filament et la détermination de la température au moyen du rapport de Bose-Einstein entre pertes et gains, (b) le refroidissement à 100 K, (c) les mesures hors-spéculaires, (d) le bombardement électronique pour ne produire que des lacunes d’oxygène et (e) l’exposition soit à l’oxygène soit à la vapeur d’eau à différentes températures. Les BGS ont été directement mis en évidence dans des conditions dans lesquelles soit Ovac soit Tiint était l’unique type de défauts de surface. Un profil schématique de la densité des électrons en excès au travers des couches de surface de TiO2(110) a été proposé et amélioré au cours du travail avec, en particulier, au moyen de la modélisation des données qui suggère leur présence en sous-surface.Les excitations de l’état solide ont été modélisées par une approche diélectrique des profils de spectres HREELS. Les BGS et la conductivité ont été représentés de manière respective par un oscillateur et un terme de Drude. Mais, alors que les BGS forment une structure définie dans la bande interdite, la signature des porteurs est moins évidente. A la différence, par exemple de l’oxyde de zinc, les valeurs élevées de la fonction diélectrique statique et de la masse effective des porteurs font que, pour les densités moyennes de porteurs, l’excitation des plasmons de surface ne produit qu’un élargissement modeste du pic quasi-élastique. Une procédure d’exaltation de la résolution est nécessaire pour révéler leur existence et leurs modes de combinaison avec les phonons. Un élément positif est que l’analyse des excitations de porteurs puisse être conduite non seulement au moyen de la partie imaginaire de la fonction diélectrique mais aussi grâce à la partie réelle et à l’écrantage résultant. La large valeur de la force d’oscillateur d’un des phonons longitudinaux permet de l’utiliser comme témoin. Situé entre celle du terme de Drude et des BGS, sa fréquence se déplace vers le bleu ou vers le rouge sous l’effet des excitations respectives des plasmons et des BGS... / The many applications of titanium dioxide TiO2, both existing and potential, have long attracted an intense research activity. In particular, TiO2 is nowadays foreseen to play a key role in environmental issues and alternative energy sources. Chemically inactive when stoichiometric, its applications mostly rely on reduced forms TiO2-x which points to properties of oxygen vacancies (Ovac) and titanium interstitials (Tiint) through which stoichiometry changes occur. The reduction of the oxide, that formally transforms Ti4+ in Ti3+, generates excess electrons that populate Ti 3d band-gap states (BGS). Central in chemistry, excess charges are also at the origin of the n-type electron conductivity of the oxide. The present work has been dealing with three central questions that are still pending, the respective role of Ovac and Tiint in the formation of BGS, the apparent contradiction between the n-type conductivity of the oxide and the deep donor character of the BGS and the nature of the electronic transport in the oxide. The origin, location and transport of excess charges were explored on rutile TiO2(110)-(1×1) by High Resolution Electron Energy Loss Spectroscopy (HREELS) measurements combined with dielectric simulations. Specific sample treatments and experimental approaches were used, including: (i) surface annealing in the 400-900 K range by exposure to a hot filament, while measuring the temperature via the Bose-Einstein loss/gain ratio; (ii) cooling down to 100 K; (iii) off-specular measurements; (iv) electron bombardment which only produces oxygen vacancies; (v) exposure to either oxygen or water vapours at different temperatures. BGS were directly evidenced in conditions in which either Ovac or Tiint were the unique type of defects of the surface. A schematic profile of the density of excess electrons through the surface region of TiO2(110) was proposed and improved throughout the manuscript by data fitting which suggested their location in the subsurface.Dielectric modelling was used to model the impact of all solid-state excitations on the shaping of HREELS spectra of reduced TiO2. It was proposed to describe BGS by an oscillator and conductivity through a Drude term. While BGS appears as a defined feature in the band gap, the signature of the carriers is less obvious. Instead of, for example zinc oxide, the large static dielectric function of the material and the high effective mass of carriers lead only to a slight broadening of the quasi-elastic peak through the excitation of surface plasmons at moderate carrier density. Enhancing apparent resolution allows glimpsing their existence and their combination modes with surface phonons. Fortunately, the carrier excitations can be tracked not only through the imaginary part of their dielectric function but also through the real part of this function and the resulting screening. Due to its very large oscillator strength, one longitudinal phonon can be used as a reporter; since its frequency lies between Drude term and BGS, it shifts upwards in energy with the occurrence of plasmon excitation and downwards with the BGS oscillator strength...

This thesis aims at increased knowledge in two fields of tribological research; both related to making currently used combustion engines greener. The first field regards the possibilities of using a boric acid fuel additive to increase fuel efficiency. The second field is about the severe wear phenomenon scuffing, which can become problematic when cargo ships are operated on low-sulphur fuel to reduce sulphuric emissions. Tribological tests were developed and performed to simulate the applications. Advanced surface analysis was performed to understand changes occurring on the outermost surface of sliding components, which affect friction and wear. Samples from engines were studied to verify the relation between the lab tests and the applications. In the case of boric acid, the coefficient of friction was below 0.02 for large parts of the tests, but varied with test parameters. The corresponding reduction in friction was up to 78% compared with tests without the additive. As an attempt to assess if the substantial fuel savings found in field tests with passenger cars (6%) can be explained by friction reduction in boundary and mixed lubricated parts of the piston assembly, assumptions were presented that would lead to fuel savings close to these 6%. Boric acid was detected on surfaces after the tests, and the tribofilm appearance depended on test parameters. The tribofilms were shown to be affected by storage time and test temperature; a finding that is vital for future studies. In the case of scuffing, mechanisms were studied and accumulation of wear debris had a significant role on scuffing initiation in the lab scale scuffing tests. Regarding the possibility to test materials scuffing resistance, there was a large scatter in the results, and thereby difficult to draw conclusions. Two new piston ring materials were identified to perform somewhat better than the currently used. In conclusion, findings that could facilitate immediate improvement of fuel efficiency of today’s combustion engine vehicles as well as findings that strengthen available hypotheses on scuffing mechanisms are presented. The latter offers improved understanding of scuffing and thereby give possibilities to counteract the higher risk associated with operation on cleaner fuel.

Organic materials with fascinating/intriguing electronic properties have been the driving force for many research activities in the past, and in particular for important progress in materials science covering both new functional materials as well as theoretical developments. In addition, charge transfer, i. e., the addition or removal of charges to or from molecules in organic solids is one route to modify and control their electronic properties. Recently, the discovery of superconductivity in several alkali metal intercalated hydrocarbon systems (picene, phenanthrene, coronene and 1,2;8,9-dibenzopentacene) with rather high transition temperatures has opened a new chapter in organic material science as well as solid-state physics. The search for a microscopic understanding of the mechanism that drives materials superconducting always has initiated a large number of scientific activities, and there are numerous examples where these activities have provided major advancement. A basic foundation of this understanding is the knowledge of the electronic properties of the material under investigation. In this context, this thesis reports first, very detailed insight into the electronic structure of both undoped as well as potassium doped picene, coronene and 1,2;8,9-dibenzopentacene using electron energy-loss spectroscopy (EELS) as main experimental method. Additionally, also photoemission spectroscopy experiments have been performed to investigate the occupied electronic density of states close to the chemical potential. In order to learn more about the electronic structure we have compared the results we obtained from EELS and photoemission spectroscopy with theoretical calculations based on Density functional theory (DFT) using the local-density approximation (LDA). We identify the peculiar case of very close lying conduction bands that upon doping harbour the electrons that form the Cooper-pairs in the superconducting state. Moreover, the presented data display substantial changes in the electronic excitation spectrum upon doping, whereas in the doped case the appearance of one new peak (for picene) and several new peaks (for coronene and 1,2;8,9-dibenzopentacene) in the former optical gap is reported. By using a Kramers–Kronig analysis (KKA) it is possible to gain information about the nature of this doping introduced excitations. In particular, in case of picene, the new low energy feature can be assigned to a charge carrier plasmon. Interestingly, this plasmon disperses negatively upon increasing momentum transfer, which deviates significantly from the traditional picture of metals based on the homogeneous electron gas. The comparison with calculations of the loss function of potassium intercalated picene shows how this finding is the result of the competition between metallicity and electronic localization on the molecular units. Furthermore, core level excitation measurements show the reduction of the lowest lying C 1s excitation feature, which clearly demonstrates that potassium intercalation leads to a filling of the conduction bands with electrons. Additionally, the measurements of potassium intercalated 1,2;8,9-dibenzopentacene clearly indicate the formation of particular doped phases with compositions K_xdibenzopentacene (x = 1, 2, 3), whereas the data suggest that K_1dibenzopentacene has an insulating ground state with an energy gap of about 0.9 eV, while K_2dibenzopentacene and K_3dibenzopentacene might well be metallic, because of the absent of an energy gap in the electronic excitation spectra. Interestingly, a comparison of the photoemission as well as EELS spectra of undoped 1,2;8,9-dibenzopentacene and pentacene reveal that the electronic states close to the Fermi level and the electronic excitation spectra of the two materials are extremely similar, which is due to the fact, that the additional two benzene rings in 1,2;8,9-dibenzopentacene virtually do not contribute to the delocalized pi molecular orbitals close to the Fermi level. This close electronic similarity is in contrast to the behavior upon potassium doping, where evidence for a Mott state has been reported in the case of pentacene. A comparison of the low energy excitation spectra of chrysene with picene (phenacenes) as well as tetracene with pentacene (acenes) crystals reveal a significant difference between the former and the latter two materials. While for the phenacenes (zigzag arrangement) the excitation onset is characterized by up to five weak excitation features with only small anisotropy and without visible Davydov splitting within the a*, b*-planes, the acene (linear arrangement) spectra are dominated by a large excitation close to the onset and a sizable Davydov splitting. The presented data show further that the spectral shape of the pentacene excitation spectrum provides clear evidence for a large admixture of molecular Frenkel-type excitons with charge-transfer excitations resulting in excited states with a significantly mixed character. This conclusion is in good agreement with recent advanced calculations which predicted a charge-transfer admixture to the lowest singlet excitation which is significantly dependent upon the length of the acene molecules. Moreover, also for picene and chrysene we observe differences which point towards an increased charge-transfer contribution to the singlet excitation spectrum in the former. Finally, investigations of the electronic properties of undoped and potassium doped chrysene, a close relative of picene, show that the doping introduced changes are in a similar range such as observed in case of picene. Interestingly, due to the analogy between the observed changes in the electronic structure upon potassium doping between chrysene and picene and further similarity in the crystal structure we speculate that chrysene is a promising candidate for another aromatic hydrocabon superconductor.

Solving for energy losses in pipe junctions has been a focus of study for many years. Although pipe junctions and fittings are at times considered "minor losses" in relation to other energy losses in a pipe network, there are cases where disregarding such losses in flow calculations will lead to errors. To facilitate these calculations, energy loss coefficients (K-factors) are commonly used to obtain energy losses for elbows, tees, crosses, valves, and other pipe fittings. When accurate K-factors are used, the flow rate and corresponding energy at any location in a pipe network can be calculated. K-factors are well defined for most pipe junctions and fittings; however, the literature documents no complete listings of K-factors for crosses. This study was commissioned to determine the K-factors for a wide range of flow combinations in a single pipe cross and the results provide information previously unavailable to compute energy losses associated with crosses. To obtain the loss coefficients, experimental data were collected in which the flow distribution in each of the four cross legs was varied to quantify the influence of velocity and flow distribution on head loss. For each data point the appropriate K-factors were calculated, resulting in over one thousand experimental K-factors that can be used in the design and analysis of piping systems containing crosses.