Le diagramme des phases du C60 continue d'être un sujet de discussion et de controverse, malgré la grande quantité de travaux expérimentaux et théoriques fait au fil des ans. Ceci est principalement dû au manque d'études in situ, a l'existence d'états désordonnés présentant des pics de diffraction très mal résolus et à la coexistence de plusieurs polytypes de faible densité. Ce manuscrit présente une étude systématique in situ des transformations hétérogènes du C60 sous haute pression et haute température dans la gamme 1-10 GPa et 300-1200 K. Afin de discriminer les poly(a)morphes de densité similaire dans des échantillons hétérogènes, nous avons utilisé une combinaison de micro-diffraction et micro-tomographie. Les échantillons ont été synthétisés dans une cellule Paris-Edimbourg et caractérisés à l'aide de diffraction des rayons X in situ en dispersion angulaire. Des images tridimensionnels à haute résolution ont été obtenus sur des échantillons trempés par la méthode de micro-tomographie de diffraction/diffusion. Cette méthode permet l'analyse 3D de l'intensité de diffusion reconstruite à partir de séries de projections 2D. Une telle analyse est non destructive et offre une grande sensibilité (0,1% en volume), une haute résolution spatiale (μm3) et peut être multimodale, fournissant des données quantitatives sur la morphologie, la densité, la composition élémentaire ou la structure des matériaux. En outre, nous décrivons le développement d'un système de micro-tomographie in situ sous haute pression et haute température en utilisant une nouvelle cellule rotative Paris-Edimbourg (RoToPEC), combinée avec le rayonnement synchrotron. La capacité à tourner complètement la chambre de l'échantillon sous charge, surmonte la contrainte d'ouverture angulaire limitée des cellules ordinaires et permet l'acquisition de projections tomographiques pour l'imagerie de plein champ ainsi que pour l'imagerie par micro-diffraction. Cette méthode innovante permet l'étude des matériaux sous conditions extrêmes de pression, température ou stress, et pourra être appliquée dans des domaines variés tels que la physique, la chimie, la science des matériaux ou la géologie. Le potentiel de cette nouvelle technique expérimentale est démontré par l'étude de la polymérisation de C60 sous haute-pression et haute température. Mots-clés: C60, diagramme de phase, diffraction, micro-tomographie, haute pression et haute température

The focus of this work is magma-crust interaction processes and associated crustal volatile release in subduction zone volcanoes, drawing on rock, mineral, and gas geochemistry as well as experimental petrology. Understanding the multitude of differentiation processes that modify an original magma during ascent to the surface is vital to unravel the contributions of the various sources that contribute to the final magmas erupted at volcanoes. In particular, magma-crust interaction (MCI) processes have been investigated at a variety of scales, from a local scale in the Vesuvius, Merapi, and Kelut studies, to a regional scale, in the Java to Bali segment of the Sunda Arc.  The role of crustal influences is still not well constrained in subduction systems, particulary in terms of the compositional impact of direct magma crust interplay. To address this shortcoming, we studied marble and calc-silicate (skarn) xenoliths, and used high resolution short timescale experimental petrology at Vesuvius volcano. The marbles and calc-silicates help to identify different mechanisms of magma-carbonate and magma-xenolith interaction, and the subsequent effects of volatile release on potential eruptive behaviour, while sequential short-duration experiments simulate the actual processes of carbonate assimilation employing natural materials and controlled magmatic conditions. The experiments highlight the efficiency of carbonate assimilation and associated carbonate-derived CO2 liberated over short timescales. The findings at Merapi and Kelut demonstrate a complex magmatic plumbing system underneath these volcanoes with magma residing at different depths, spanning from the mantle-crust boundary to the upper crust. The erupted products and volcanic gas emissions enable us to shed light on MCI-processes and associated volatile release in these systems. The knowledge gained from studying individual volcanoes (e.g., Merapi and Kelut) is then tested on a regional scale and applied to the entire Java and Bali arc segment. An attempt is presented to distinguish the extent of source versus crustal influences and establish a quantitative model of late stage crustal influence in this arc segment. This thesis therefore hopes to contribute to our knowledge of magma genesis and magma-crust interaction (MCI) processes that likely operate in subduction zone systems worldwide.

The aim of this study is to synthesize a material with high thermal conductivity and a low coefficient of thermal expansion (CTE), useful as a heat sink. Carbon nanofibres (CNF) are first coated with copper by an electroless plating technique and then sintered to a solid sample by either spark plasma sintering (SPS) or hot pressing (HP). The final product is a carbon nanofibre reinforced copper composite. Two different fibre structures are considered: platlet (PL) and herringbone (HB). The influence of the amount of CNF reinforcement (6-24 %wt), on the thermal conductivity and CTE is studied. CNF has an excellent thermal conductivity in the direction along the fibre while it is poor in the transverse direction. The CTE is close to zero in the temperature range of interest. The adhesion of Cu to the CNF surface is in general poor and thus improving the the wetting of the copper by surface modifications of the fibres are of interest such that thermal gaps in the microstructure can be avoided. The poor wetting results in CNF agglomerates, resulting in an inhomogeneous microstructure. In this report a combination of three different types of surface modifications has been tested: (1) electroless deposition of copper was used to improve Cu impregnation of CNF; (2) heat treatment of CNF to improve wetting; and (3) introduction of a Cr buffer layer to further enhance wetting. The obtained composite microstructures are characterized in terms of chemical composition, grain size and degree of agglomeration. In addition their densities are also reported. The thermal properties were evaluated in terms of thermal diffusivity, thermal conductivity and CTE. Cr/Cu coated platelet fibres (6wt% of CNF reinforcement) sintered by SPS is the sample with the highest thermal conductivity, ~200 W/Km. The thermal conductivity is found to decrease with increasing content of CNFs.

This work focuses on crustal interaction in magmatic systems, drawing on experimental petrology and elemental and isotope geochemistry. Various magma-chamber processes such as magma-mixing, fractional crystallisation and magma-crust interaction are explored throughout the papers comprising the thesis. Emphasis is placed on gaining insights into the extent of crustal contamination in ocean island magmas from the Canary Islands and the processes of magma-crust interaction observed both in nature and in experiments. This research underscores that the compositions of ocean island magmas, even primitive types which are classically used as probes of the mantle, are susceptible to modification by crustal contamination. The principal mechanisms of contamination identified from work on both Tenerife and Gran Canaria (Canary Islands) are assimilation and partial melting of the pre-existing island edifice and intercalated sediments by newly arriving magma (i.e. “island recycling”). The information that we can gain from studying solidified magma and entrained crustal xenoliths concerning the rates and mechanisms of crustal assimilation is, however, limited. To address this shortcoming, a series of time-variable crustal carbonate assimilation experiments were carried out at magmatic pressure and temperature using natural materials from Merapi volcano, Indonesia. A temporally constrained reaction series of carbonate assimilation in magma has hence been constructed. The experiments were analysed using in-situ techniques to observe the progressive textural, elemental, and isotopic evolution of magma-carbonate interaction. Crucially, carbonate assimilation was found to liberate voluminous crustally-derived CO2 on a timescale of only seconds to minutes in the experiments. This points to the role of rapid crustal degassing in volcanic volatile budgets, and, pertinently, in magnifying hazardous volcanic behaviour. This thesis, therefore, delivers detailed insights into the processes of magma-crust interaction from experiments and geochemistry. The outcomes confirm that crustal processes are significant factors in both, i) ocean island magma genesis, and ii) magma differentiation towards compositions with greater explosive potential which can, in turn, manifest as hazardous volcanism. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 707

The touchscreen user interface is an inherently dynamic device that is becoming ubiquitous. The touchscreen’s ability to adapt to the user’s needs makes it superior to more traditional haptic devices in many ways. Most touchscreen devices come with a very large array of sensors already included in the package. This gives engineers the means to develop human-machine interfaces that are very intuitive to use. This thesis presents research that was done to develop a best touchscreen interface for driving an industrial crane for novice users. To generalize the research, testing also determined how touchscreen interfaces compare to the traditional joystick in highly dynamic tracking situations using a manual tracking experiment. Three separate operator studies were conducted to investigate touchscreen control of cranes. The data indicates that the touchscreen interfaces are superior to the traditional push-button control pendent and that the layout and function of the graphical user interface on the touchscreen plays a roll in the performance of the human operators. The touchscreen interface also adds great promise for allowing users to navigate through interactive textbooks. Therefore, this thesis also presents developments directed at creating the next generation of engineering textbooks. Nine widgets were developed for an interactive mechanical design textbook that is meant to be delivered via tablet computers. Those widgets help students improve their technical writing abilities, introduce them to tools they can use in product development, as well as give them knowledge in how some dynamical systems behave. In addition two touchscreen applications were developed to aid the judging of a mechanical design competition.

<p>Since the inception of hyperpolarized 129Xe MRI, the field has yearned for more efficient production of more highly polarized 129Xe. For nearly all polarizers built to date, both peak 129Xe polarization and production rate fall far below theoretical predictions. This thesis sought to develop a fundamental understanding of why the observed performance of large-scale 129Xe hyperpolarization lagged so badly behind theoretical predictions.</p><p> This is done by thoroughly characterizing a high-volume, continuous-flow polarizer using optical cells having three different internal volumes, and employing two different laser sources. For each of these 6 combinations, 129Xe polarization was carefully measured as a function of production rate across a range of laser absorption levels. The resultant peak polarizations were consistently a factor of 2-3 lower than predicted across a range of absorption levels, and scaling of production rates deviated badly from predictions based on spin exchange efficiency.</p><p> To bridge this gap, we propose that paramagnetic, activated Rb clusters form during spin exchange optical pumping (SEOP), and depolarize Rb and 129Xe, while unproductively scattering optical pumping light. When a model was built that incorporated the effects of clusters, its predictions matched observations for both polarization and production rate for all 6 systems studied. This permits us to place a limit on cluster number density of <2 × 109 cm-3.</p><p> The work culminates with deploying this framework to identify methods to improve polarization to above 50%, leaving the SEOP cell. Combined with additional methods of preserving polarization, the polarization of a 300-mL batch of 129Xe increased from an average of 9%, before this work began, to a recent value of 34%.</p><p> We anticipate that these developments will lay the groundwork for continued advancement and scaling up of SEOP-based hyperpolarization methods that may one day permit real-time, on-demand 129Xe MRI to become a reality.</p> / Dissertation

In the past couple of decades, the discovery that iron is a limiting nutrient in large regions of the ocean has spurred much research into characterizing the biogeochemical controls on iron cycling. While Fe(II) is soluble at circumneutral pH, it readily oxidizes to Fe(III) in the presence of oxygen. Fe(III) is highly insoluble at circumneutral pH, presenting organisms with a bioavailability paradox stemming from the physiological challenge of using a solid phase mineral for assimilatory or dissimilatory purposes. Interestingly, dissolved organic-Fe(III) complexes can be stable in seawater in the presence of oxygen, and an active flux of these complexes has recently been measured in estuarine sediments. Their sources and biogeochemical role, however, remain poorly understood. In this work, a suite of field and laboratory techniques were developed to quantify diagenetic processes involved in the remineralization of carbon in marine sediments in situ, investigate the role of these organic-Fe(III) complexes in sediment biogeochemistry, and characterize the composition of the ligands possibly involved in the solubilization of Fe(III) in marine sediments. The first-of-its-kind in situ electrochemical analyzer and HPLC was used to better constrain diagenetic processes that may lead to the formation of dissolved organic-Fe(III) complexes in the Altamaha estuary and Carolina slope. An intensive study of the Satilla River estuary reveals that dissimilatory iron-reduction contributes to the formation of sedimentary organic-Fe(III) complexes, which are demonstrated to serve as an electron acceptor in subsequent incubations with a model iron-reducing microorganism. Similar observations in deep-sea slope and abyssal plain sediments fed by the Mississippi and Congo Rivers suggest that dissimilatory iron reduction may represent an important component of carbon remineralization in river-dominated ocean margin sediments that may be currently underestimated globally. To confirm that these organic-Fe(III) complexes are produced during microbial iron reduction, novel separation schemes were developed to extract and identify Fe(III)-binding ligands from sediment pore waters. Preliminary results reveal the presence of a few select low-molecular weight compounds in all pore waters extracted, suggesting they might be endogenous ligands secreted by iron-reducing bacteria to non-reductively dissolve Fe(III) minerals prior to reduction.

In dieser Arbeit wurde der Einsatz von Amberlite XAD 7 HP imprägniert mit Di-(2-ethylhexyl)phosphorsäure als Solvent imprägniertes Harz für die Trennung von Ionen Seltener Erdelemente in einer Trennsäule untersucht. Mittels Batchversuchen wurden die Extraktionsisothermen und Extraktionskinetiken für verschiedene Seltene Erdelemente an imprägniertem Amberlite XAD 7 HP bestimmt und der Einfluss der Amberlitepartikelgröße auf diese Isothermen und Kinetiken untersucht. Versuche an der Trennsäule zeigten einen großen Einfluss des Volumenstroms des Elutionsmittels und der Amberlitepartikelgröße auf den Trennerfolg eines binären Gemischs Seltener Erdelemente. Im Gegensatz zu den unzerkleinerten Amberlitepartikeln ist es durch den Einsatz von zerkleinerten Amberlitepartikeln möglich gewesen, ein Cerium-Lanthan-Gemisch zu trennen. Die Regenerationsfähigkeit und die Wiederverwendbarkeit des hergestellten Solvent imprägnierten Harzes konnte gezeigt werden.:Inhaltsverzeichnis 1 Einleitung und Zielstellung .............................................................................. 1 2 Stand von Wissenschaft und Technik ............................................................. 3 2.1 Seltene Erdelemente ................................................................................ 3 2.1.1 Vorkommen und Anwendungsgebiete von Seltenen Erdelementen .. 4 2.1.2 Chemische und physikalische Eigenschaften von Seltenen Erdelementen ..................................................................................... 7 2.1.3 Abbau und Aufbereitung von Seltenen Erdelementen ..................... 10 2.1.4 Verfahren für die Trennung von Gemischen Seltener Erdelemente . 11 2.1.5 Alternative und umweltschonendere Verfahren für die Trennung von Gemischen Seltener Erdelemente ............................................. 18 2.2 Zerkleinern von polymeren Materialien .................................................. 22 2.2.1 Zerkleinerung von Ionentauschern in verschiedenen Mühlen .......... 23 2.2.2 Zerkleinern von polymeren Ionentauscherpartikeln in einer Trommelmühle ................................................................................. 25 2.3 Adsorptionsisotherme/Extraktionsisotherme .......................................... 27 2.4 Einführung in die Extraktionschromatographie ....................................... 31 2.4.1 Grundlagen der Extraktionschromatographie ................................... 32 2.4.2 Solvent imprägnierte Harze und Levextrel-Harze - spezielle Formen von Trägermaterialien ......................................................... 45 2.4.2.1 Herstellung und Eigenschaften von Solvent imprägnierten Harzen ................................................................................. 47 2.4.2.2 Eigenschaften und Herstellung von Levextrel-Harzen .......... 51 2.4.2.3 Einsatz von Solvent imprägnierten Harzen und LevextrelHarzen in der Metallextraktion ............................................. 52 2.4.2.4 Probleme bei dem Einsatz von Solvent imprägnierten Harzen ................................................................................. 56 IV 2.4.3 Einfluss der Struktur des Trägermaterials und der Arbeitsbe- dingungen auf die Trennleistung einer Trennsäule .......................... 57 2.4.4 Einsatz der Extraktionschromatographie für die Trennung von Gemischen Seltener Erdelemente ................................................... 60 2.4.5 Mechanismus bei der Trennung von Seltenen Erdelementen mittels Extraktionschromatographie und D2EHPA ............................ 64 3 Experimentelles Arbeiten .............................................................................. 67 3.1 Verwendetet Materialien ......................................................................... 67 3.1.1 Trägermaterialien ............................................................................. 67 3.1.2 Stationäre Phase.............................................................................. 71 3.1.3 Seltene Erdelemente ........................................................................ 72 3.2 Verwendete Apparaturen und Messgeräte ............................................. 72 3.2.1 Messmethoden für die Partikelcharakterisierung ............................. 72 3.2.2 Bestimmung der Elementkonzentration von wässrigen Proben mittels ICP OES ............................................................................... 75 3.2.3 Aufbau und Funktionsweise der Trennsäule .................................... 79 3.3 Durchführung von Versuchen zur Charakterisierung der Extraktionsmaterialien und zur Trennung binärer Gemische Seltener Erdelemente ..... 82 3.3.1 Waschung von Amberlite XAD 7 HP ................................................ 84 3.3.2 Zerkleinern und Klassieren von Amberlite XAD 7 HP ...................... 84 3.3.3 Imprägnierung von Amberlite XAD 7 HP .......................................... 85 3.3.4 Batchversuche zur Ermittlung geeigneter Parameter, Extraktionskinetiken, Extraktionskapazitäten und Säurekonzentrationen .......... 86 3.3.5 Trennung von Ionen Seltener Erdelemente mittels Trennsäule ....... 89 3.3.6 Prüfung auf Reproduzierbarkeit der Versuche an der Trennsäule ... 93 3.3.7 Prüfung auf Wiederverwendbarkeit des Extraktionsmaterials .......... 93 3.3.8 Hydrophobierung von hydrophilen Oberflächen ............................... 94 4 Ergebnisse .................................................................................................... 96 4.1 Zerkleinerung des Trägermaterials Amberlite XAD 7 HP ....................... 96 V 4.2 Reaktionsmechanismus von Ionen Seltener Erdelemente bei der Extraktion ............................................................................................. 100 4.3 Imprägnierung des Trägermaterials Amberlite XAD 7 HP .................... 101 4.4 Charakterisierung des Trägermaterials Amberlite XAD 7 HP vor und nach der Imprägnierung mit D2EHPA ................................................... 103 4.4.1 Unzerkleinertes Trägermaterial Amberlite XAD 7 HP ..................... 103 4.4.2 Zerkleinertes Trägermaterial Amberlite XAD 7 HP ......................... 107 4.4.3 Auswertung der 3D-Röntgenmikroskopie einer mit Neodym beladenen Amberliteschüttung ........................................................... 110 4.5 Vorversuche zur Ermittlung von geeigneten Versuchsparametern und zur Bestimmung der Kapazitäten des Extraktionsmaterials ........... 112 4.5.1 Ermittlung des optimalen pH-Werts für die Trennung von Ge- mischen Seltener Erdelemente ...................................................... 112 4.5.2 Ermittlung der optimalen Schüttelzeit für maximale Extraktionskapazitäten ..................................................................................... 113 4.5.3 Extraktionskinetik ........................................................................... 115 4.5.4 Ermittlung von Extraktionsisothermen ausgewählter Seltener Erdelemente ................................................................................... 118 4.5.5 Bestimmung der Trennfaktoren von binären Gemischen Seltener Erdelemente mittels imprägniertem Amberlite XAD 7 HP .............. 124 4.5.6 Variation der Stoffmengenkonzentration des Elutionsmittels Salzsäure für die Trennung von Gemischen Seltener Erdelemente ..... 127 4.5.7 Typische Störkomponenten ........................................................... 129 4.6 Charakterisierung der Trennsäule ........................................................ 130 4.6.1 Überprüfung der Reproduzierbarkeit der Ergebnisse ..................... 131 4.6.2 Variation des Volumenstroms der mobilen Phase in der Trennsäule ..................................................................................... 132 4.6.3 Prüfung der Wiederverwendbarkeit des Extraktionsmaterials ........ 137 4.6.4 Lokale Masseverteilung der Seltenen Erdelemente in der Trennsäule ..................................................................................... 140 VI 4.7 Trennung binärer Gemische Seltener Erdelemente mittels unzerkleinertem imprägniertem Amberlite XAD 7 HP ........................... 146 4.8 Trennung binärer Gemische Seltener Erdelemente mittels zer- kleinertem imprägniertem Amberlite XAD 7 HP .................................... 152 4.9 Untersuchung zum Trennverhalten eines Eisen-Lanthan-Gemischs (mögliche Störkomponenten) ............................................................... 159 4.10 Weitere Trägermaterialien .................................................................... 162 4.10.1 Lewatit VP OC 1026 ....................................................................... 162 4.10.2 Celite-512 ....................................................................................... 169 4.10.3 Divergan RS ................................................................................... 171 4.10.4 Vergleich aller eingesetzten Trägermaterialien .............................. 173 5 Zusammenfassung und Ausblick ................................................................ 175 6 Literaturverzeichnis ..................................................................................... 178 Abbildungsverzeichnis .................................................................................... 197 Tabellenverzeichnis ........................................................................................ 208 Anhang ........................................................................................................... 210

Métodos de predição ab initio de estrutura de proteínas (PSP) buscam prever, baseando-se em primeiros princípios, a estrutura tridimensional que uma dada seqüência de aminoácidos irá adotar no espaço. Os métodos de predição ab initio atualmente possuem aplicações biotecnológicas que envolvem desde a criação de novas proteínas, o auxílio no desenho racional de fármacos (estrutura do receptor), o refinamento de modelos teóricos e a obtenção de estruturas a partir de dados experimentais incompletos. Entretanto, a predição envolve um problema de otimização que lida com milhares de graus de liberdade e está associado à hipersuperfícies de energia extremamente complexas o que torna o problema difícil de ser tratado computacionalmente. Neste trabalho utilizamos um modelo tridimensional de proteínas simplificado (modelo hidrofóbico-polar, HP) para reduzir os custos computacionais associados ao problema de PSP de modo que uma metodologia de otimização, robusta e eficiente, baseada em algoritmos genéticos, fosse desenvolvida mais rapidamente. Em seguida a metodologia foi adaptada para um modelo com descrição atômica que utiliza um campo de forças clássico como função de energia. Durante o desenvolvimento foram implementadas e analisadas várias estratégias para o problema. Foi descrita uma nova abordagem, baseada em crowding, para a manutenção da diversidade na população que resulta na obtenção simultânea de múltiplas soluções. A metodologia para o modelo HP foi aplicada a 35 seqüências disponíveis na literatura e os resultados comparativos mostraram que o algoritmo genético desenvolvido é superior a outros algoritmos evolutivos publicados, e comparável a métodos especializados. A metodologia para o modelo atômico foi inicialmente testada em poli-alaninas e em seguida em cinco outras proteínas de maior complexidade. Foram encontradas estruturas apresentando RMSDs entre 2,0 e 6,7 Å, em relação à estrutura determinada experimentalmente. O algoritmo genético se mostrou superior a outros métodos semelhantes, em termos de custo computacional. Os resultados obtidos mostram que as estratégias de otimização envolvendo a busca por múltiplos mínimos possuem duas grandes vantagens. A primeira delas está em uma investigação mais efetiva de uma hipersuperfície complexa aumentando a probabilidade de se encontrar soluções ótimas (de mais baixa energia); a segunda delas está no aumento da probabilidade de se obter estruturas próximas daquelas determinadas experimentalmente mesmo quando estas não são o mínimo global da hipersuperfície de energia investigada.

This thesis deals with software testing and its possible automation and compares the pros and cons of automated testing with manual testing. In the automated approach is introduced tool for automated testing HP QuickTest Professional (HP QTP). The main objective is to analyze the advantages of using this tool in conditions of a real project, based on predefined criteria. In the theoretical section I introduce basic terms within the field of software testing and identify testing in the software development process. A comparison of manual and automated approach to software testing and introduction of tool HP QTP for automated tests follows. Target of practical part is to analyze the advantages of automation by using HP QTP on a real project according to defined criteria and recommend for what conditions the automation in this case worthwhile. In the practical part is also created manual which describing the basic functionality of HP QTP, which is demonstrated on examples. Manual, which is also the output of this work, has to help testers to quickly understand the work with this tool and therefore better plan process of tests automation.