Rozprawy doktorskie na temat „Volatiles Elements”

Methylzinc tetrahydroborate, [MeZnBH₄], has been prepared by two routes and the structure of the solid determined by X-ray crystallography to reveal helical polymers in which MeZn and BH₄ units alternate. The latter functions as a bidentate ligand with respect to each of the adjacent metal atoms. Investigation by mass spectrometry and matrix isolation shows that the vapour consists of an equilibrium mixture of monomeric and dimeric species. The pattern of infrared bands for the monomer is characteristic of a bidentate BH₄ group, a finding consistent with the results of DFT calculations. Disproportionation into [Me₂Zn] and [Zn(BH₄)₂] is a common feature of the chemistry of methylzinc tetrahydroborate, although it has been possible to isolate and characterize the adduct [MeZnBH₄.SMe₂]. The reaction between [B₄H₁₀ and [Me₂Zn] in the gas phase affords colourless acicular crystals of [(MeZn)₂B₃H₇] in yields of ca. 10%. This compound has been characterized by chemical analysis and by NMR and vibrational spectroscopy. X-ray crystallography reveals that the product is a dimer, [(MeZn)₂B₃H₇]₂, featuring two distinct zinc environments. Two B₃H₇ZnNe ligands, formally derived from B₃H₈ by replacement of a µ₂-H by a µ₂-ZnMe unit, each function in a bis(bidentate) manner linking together two other MeZn centres through pairs of Zn-H-B bridges. The structures of several aluminium tetrahydroborates in the solid phase have been investigated by X-ray diffraction. The structure of dimethylaluminum tetrahydroborate has been shown to consist of helical polymeric chains in which Me₂-Al and BH₄ units alternate. Here, too, the BH₄ groups exhibit bidentate ligation with respect to each of the adjacent metal atoms, although the degree of interaction between the metal centre and the BH₄ group is somewhat less than in [MeZnBH₄ ]. Solid aluminium tris(tetrahydroborate) exhibits two phases with a transition temperature in the range 180-195 K. Each phase is made up of discrete Al(BH ₄ )₃ units, the principal differences relating to the packing of the individual molecules. In the a phase the Al(BH ₄ )₃ molecules display an angle of 78.2° between the AlB₃ and Al(µ-H)₂ planes and are disposed about a 2₁ crystallographic screw axis; in the ß phase the molecular units conform to D_3h symmetry. Dimethylindium octahydrotriborate, [Me₂ lnB₃ H₈ ], has been synthesized by the reaction between trimethylindium and tetraborane(10) and characterized by chemical analysis and by NMR and vibrational spectroscopy. X-ray diffraction of a single crystal reveals that the solid consists of [Me₂ lnB₃ H₈] units, although there is evidence of charge separation in the sense [Me₂ln]⁺[B₃ H₈ ]^- and of secondary interaction between terminal hydrogen atoms and adjacent indium centres. The infrared spectrum of the matrix-isolated vapour is consistent with a monomeric structure similar to that of [Me₂ AlB₃ H₈].

La présence de magmas en profondeur permet de contraindre des processus géologiques passés et actuels. Ces magmas (i.e. liquides silicatés) participent aux cycles géochimiques des éléments volatils comme vecteur de matière.Nous étudions deux éléments volatils complémentaires : l'iode (I), un halogène, et le xénon (Xe), un gaz rare. Leur système radioactif éteint 129I/129Xe (T1/2 = 15.7Ma) est utilisé pour dater les processus hadéens et la formation de l'atmosphère, issu de l'évolution d'un océan magmatique. Or on connait peu le comportement de l'iode et du xénon dans les magmas en profondeur à haute pression et température.Notre protocole expérimental vise l'étude de l'incorporation de l'iode et du xénon et de leur solubilité dans les magmas. Pour étudier l'incorporation, la structure des silicates liquides a été caractérisée par diffraction de rayons X avec des expériences in situ réalisées dans des cellules à enclumes de diamant et dans des presses Paris-Édimbourg. Les teneurs de solubilité de l'iode et du xénon ainsi que l'eau ont été mesurés par les méthodes PIXE et ERDA.À hautes pressions, l'iode possède une forte solubilité (quelques %pds) dans les magmas. Les résultats préliminaires sur son incorporation dans du basalte montrent que l'iode ne formerait pas des liaisons covalentes. À haute pression et température (T&gt;300°C - P&gt;1GPa), le xénon forme une liaison covalente Xe-O avec les oxygènes des anneaux de 6 tétraèdres SiO44-. Le xénon a une solubilité élevée dans les magmas (4pds% - 1600°C - 3.5GPa).Les modèles de datation et des cycles géochimiques de l'iode et du xénon doivent être revus en tenant compte de leur comportement différentiel dans les magmas<br>The presence of magmas at depth helps to constrain past and actual geological processes. Magmas (i.e. silicate melts) participate in geochemical cycles of volatile elements, as vectors of chemical transfers. We study two complementary volatile elements: iodine (I), a halogen, and xenon (Xe), a noble gas. Their extinct 129I/129Xe isotopic system (half-life of 15.7Ma) is used to date Hadean processes and Earth’s atmosphere formation since the atmosphere originated from the Magma Ocean’s evolution. However, little is known about the behavior of both iodine and xenon in silicate melts at depth, under HT and HP conditions. Our experimental protocol aims at elucidating the incorporation process of xenon and iodine in silicate melts, and their solubility. To understand the incorporation of iodine and xenon in magmas, the structure of silicate melts was investigated by in situ diamond anvil cells and Paris-Edinburgh press experiments coupled with X-ray diffraction characterization. Iodine and xenon’s solubility, along with water content are obtained by PIXE and ERDA methods using a nuclear microprobe. At high pressure, iodine has a high solubility (about few wt.%) in magmas. Preliminary results on iodine incorporation in basaltic melt show an absence of covalent bond. At high pressure and temperature conditions (T&gt;300°C – P&gt;1GPa), xenon forms a Xe-O covalent bond with the oxygens of the 6-membered-rings of the melt network. Its solubility in silicate melts is also high (about 4wt.% in haplogranite melts at 1600°C and 3.5GPa). Considering the xenon and iodine differential behavior in melts at depth, a revision of dating models in xenon and iodine cycles must be considered

Thesis: Ph. D., Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2018.<br>Cataloged from PDF version of thesis.<br>Includes bibliographical references.<br>This thesis investigates the timing and source(s) of water and volatile elements to the inner solar system by studying the basaltic meteorites angrites and eucrites. In chapters 2 and 3, I present the results from angrite meteorites. Chapter 2 examines the water and volatile element content of the angrite parent body and I suggest that some water and other volatile elements accreted to inner solar system bodies by ~2 Myr after the start of the solar system. Chapter 3 examines the D/H of this water and I suggest it is derived from carbonaceous chondrites. Chapter 4, 5, 6, and 7 addresses eucrite meteorites. Chapter 4 expands on existing models to explain geochemical trends observed in eucrites. In Chapter 5, I examine the water and F content of the eucrite parent body, 4 Vesta. In chapter 6, I determine the source of water for 4 Vesta and determine that carbonaceous chondrites delivered water to this body. Chapter 7 discusses degassing on 4 Vesta while it was forming.<br>by Adam Robert Sarafian.<br>Ph. D.

Les comètes sont parmi les corps les plus primitifs et inaltérés de notre système solaire. Leur étude peut fournir un aperçu unique de la composition chimique du système solaire primitif. De plus, en raison de leur nature riche en élément volatils, les comètes ont probablement joué un rôle crucial dans l'apport d'éléments pré-biotiques (H, C, N et O) et de matières organiques à la Terre primitive. Comprendre comment se forment les comètes peut donc fournir une mine d'informations sur l'évolution de la composition des éléments volatils dans le système solaire, depuis le nuage moléculaire pré-solaire jusqu'à la formation des planètes telluriques. Des décennies d'études cométaires, et la récente mission Rosetta de l'ESA sur la comète 67P/Churyumov-Gerasimenko (67P/C-G), ont démontré que les espèces volatiles piégées dans les comètes ont une composition distincte de tout autre réservoir connu du système solaire. L'azote cométaire, en particulier, présente de forts enrichissements en isotope 15N. L'origine de ces enrichissements reste incertaine, reflétant potentiellement la présence de processus permettant de produire de forts fractionnements isotopiques d'un gaz nébulaire initial pauvre en 15N, ou l'héritage d'un réservoir isotopique riche en 15N inconnu. Au cours de cette thèse, j'ai développé une expérience pour former des glaces cométaires (c'est-à-dire des glaces riches en eau formées à des températures et des pressions très basses), avec l'objectif principal d'explorer comment les éléments volatils (l'azote et les gaz nobles) sont incorporés dans les glaces cométaires à partir de la nébuleuse proto-solaire. Différentes températures de formation (de 28K à 80K) et conditions d'irradiation ont été testées afin d'étudier les paramètres reproduisant le plus fidèlement la composition de la comète 67P/C-G. Les analogues de glace cométaires formés expérimentalement autour de 70K ont des abondances relatives d'azote et de gaz nobles plus proches de celles mesurées dans 67P/C-G que les analogues formés à plus basses températures (≤ 60K). De plus, j'ai mis en évidence que les processus d'incorporation de l'azote et des gaz nobles dans la glace et leur libération ultérieure ne produisent pas de variations isotopiques significatives. Cela indique que les signatures isotopiques des comètes ont très probablement été héritées de leur environnement de formation, et ne résultent pas de processus de fractionnements isotopiques pendant la formation/sublimation de la glace. Enfin, j'ai également étudié l'effet que l'irradiation UV peut avoir sur la composition des gaz piégés dans la glace cométaire. L'irradiation pendant et après le dépôt de glace n'a que peu d'effet sur la composition isotopique des espèces volatiles piégées. Cependant, l'irradiation de la surface de la glace a un effet majeur sur le schéma de libération des gaz piégés. Une glace irradiée conserve ses éléments volatils piégés à des températures supérieures à la température de transition de la glace amorphe à cristalline (120-140K), à l'inverse d'une glace non-irradiée. La rétention prolongée des gaz piégés dans les glaces cométaires irradiées peut avoir des implications majeures sur la capacité des comètes à contribuer à l'apport d'éléments volatils aux planètes du système solaire interne<br>Comets represent some of the most pristine and unprocessed bodies in our solar system. As such, their analysis can provide a unique insight into the chemical makeup of the early Solar System. Furthermore, due to their volatile-rich nature, comets may have played an important role in delivering volatile elements (e.g., H, C, N, O) and organic materials to early Earth. Understanding how comets form can therefore provide a wealth of information on how the composition of volatile elements evolved in the solar system, from the pre-solar molecular cloud up until the formation of the terrestrial planets. Decades of cometary studies, and the recent ESA Rosetta mission to comet 67P/Churyumov-Gerasimenko (67P/C-G), have demonstrated that volatile species trapped in comets have a composition that is distinct from any other known reservoir in the Solar System. Cometary nitrogen, in particular, shows strong enrichments in the rare 15N isotope. The origin of these enrichments remains unclear, potentially reflecting the isotopic fractionation of an initial 15N-poor nebular gas, or inheritance from an unknown isotopic reservoir. During this PhD, I have developed an experimental setup to form cometary ices (i.e., water-rich ices formed at very low temperatures and pressures), with the overarching objective of exploring how volatile elements (including N and noble gases) were incorporated into cometary ice during water condensation from the protosolar nebula. Different temperatures of formation (from 28K to 80K) and irradiation conditions have been tested in order to investigate the conditions that best reproduce the actual volatile composition of comet 67P/C-G. It was found that condensing cometary ice analogues at temperatures ~70K is best able to reproduce the nitrogen and noble gas abundances measured in 67P/C-G. Moreover, we discovered that the incorporation of nitrogen and noble gases into, and subsequent release from, cometary ices does not produce significant isotope variations, indicating that isotope signatures in comets were most likely inherited from their environment of formation rather than the result of fractionation during ice formation. Finally, I also investigated the effect that UV irradiation can have on the composition of volatiles trapped within cometary ice. Irradiation during and after ice deposition was found to not have a significant effect on the isotopic composition of the trapped volatile species. However, it was discovered that irradiating the surface of the ice had a major effect on the release pattern of trapped volatiles, with the ice being retentive of trapped volatiles even after the amorphous-to-crystalline ice transition (120-140K), temperatures at which point all trapped volatiles are released from non-irradiated ice. The enhanced retention of volatiles in irradiated cometary ice may have major implications on the potential for comets to deliver volatile elements to the inner solar system

Ce projet de thèse s’articule autour de l’étude du fractionnement isotopique de l’étain (Sn) et du zinc(Zn) dans le système solaire. Etant deux éléments modérément volatils, les isotopes de ces éléments sont sensibles aux processus d’évaporation et de condensation. L’étude des fractionnements isotopiques du Zn et de l’Sn permet donc de mieux comprendre l’appauvrissement en éléments volatils des planètes telluriques et des météorites. Une méthode de mesure de composition isotopique en Zn a été développée au cours de la thèse. Le premier objectif a ensuite été de déterminer la composition isotopique en Sn et Zn du manteau global de la Terre. Pour cela, il a été nécessaire de comprendre le comportement des isotopes de ces deux systèmes au cours des processus magmatiques grâce à des mesures isotopiques et au développement de modèles associés. Ces derniers nécessitent, pour être quantitatifs, la connaissance des facteurs de fractionnement isotopiques, ce qui n’existait pas jusqu’ici pour les isotopes de l’étain. Ils ont été déterminés par deux méthodes indépendantes : la spectroscopie NRIXS et la spectrométrie de masse associée à des expériences d’équilibres métal-silicate. A partir de ces résultats, il a été possible de discuter des implications quant à la formation du noyau terrestre et sur la composition de la Terre globale<br>This project focuses on the study of the isotopic fractionation of tin (Sn) and zinc (Zn) in the solar system. Being two moderately volatile elements, the isotopes of these elements are sensitive to evaporation and condensation processes. Therefore, the study of Zn and Sn isotope fractionation provides tools to better understand volatile element depletion in terrestrial planets and meteorites. A method for measuring Zn isotope composition was developed during the thesis. The first objective of this thesis was to determine the Sn and Zn isotope compositions of the Earth’s mantle. To do that, the first step consisted in understanding the behavior of both isotope systems during magmatic processes using isotope measurements and modelling of partial melting and fractional crystallization. In order to develop a quantitative model, we determined the isotope fractionation factors (which were unknown in the case of Sn) using two independent methods: NRIXS spectroscopy and mass spectrometry associated with metal-silicate equilibrium experiments. Based on these results, we discussed the implications concerning core formation on Earth and the Sn isotope composition of the bulk Earth

Hydride generation technique is frequently used for the detection of elements as As, Se, Sb, Sn, Bi, Ge, Te and Pb that form volatile hydrides in solution using a reductant. In this study, a novel quartz trap for on-line preconcentration of volatile analyte species was designed. Pb, Sb and Cd were selected as analyte elements and chemical vapour generation technique was employed for generation of their volatile species in flow systems. The trapping medium was formed by external heating of either the inlet arm of the quartz tube atomizer or a separate cylindirical quartz tube. Generated analyte species were trapped on quartz surface heated to the collection temperature and the collected species were revolatilized when the trap was heated further to releasing temperature and hydrogen gas was introduced in the trapping medium. The conventional quartz T-tube and multiple microflame quartz tube were employed as atomizers. The influence of relevant experimental parameters on the generation, collection and revolatilization efficiencies was investigated. Optimum conditions, performance characteristics of the trap and analytical figures of merit are presented. Experimental design was used for optimizations in some cases. Standard reference materials were analyzed to assess the accuracy of the proposed method. For a collection period of 1.0 minute for Pb, 2.0 minutes for Sb and 3.0 minutes for Cd, 3&amp<br>#963<br>limit of detections, in pg ml-1, were 19, 3.9 and 1.8, respectively. In cases of Sb and Cd, the limits of detections obtained are the same as the best attained with in-situ trapping in graphite furnaces.

La formation des noyaux planétaires métalliques est un évènement majeur pour l’évolution des propriétés physico-chimiques des planètes telluriques telles que nous les connaissons aujourd’hui. En effet, l’abondance des éléments sidérophiles (i.e. qui ont des affinités chimiques avec les phases métalliques) dans les manteaux planétaires s’explique par les conditions dans lesquelles se sont séparées les phases métalliques et silicatées. Au premier rang de ces conditions se trouvent la pression, la température et la fugacité d’oxygène. La distribution des éléments dans le noyau et le manteau ne peut en effet s’expliquer que pour un équilibre obtenu dans un océan magmatique profond, donc à haute pression et haute température ; et dans des conditions d’oxydo-réduction variables, dont l’évolution la plus probable est de passer d’un état réduit à un état oxydé. Un autre paramètre important est la présence ou non d’eau dans l’océan magmatique primitif. En effet, nous disposons de plus en plus d’arguments permettant d’expliquer l’arrivée des éléments volatils, notamment l’eau, pendant l’accrétion, à partir de briques élémentaires qui contiennent ces éléments. Si l’eau est présente tout au long de l’accrétion, et donc pendant la ségrégation du noyau, elle peut donc avoir un effet sur ce dernier phénomène. Dans cette hypothèse, nous avons mené des expériences de haute pression et haute température permettant de modéliser expérimentalement la formation du noyau en condition hydratée. Ces expériences nous ont permis de montrer que la présence d’eau a un effet sur l’évolution de l’état d’oxydation des manteaux planétaires. Cette évolution oxydo-réductive nous a permis de contraindre des modèles d’accrétion basés sur un mélange de chondrites EH et CI, qui confirment des modèles construits à partir de données isotopiques. Ces modèles nous ont permis de contraindre les concentrations primitives maximum en eau probables sur Terre (1,2-1,8 % pds.) et sur Mars (2,5-3,5 % pds.). D’autre part, nos avons mis en évidence le caractère lithophile (i.e. qui a des affinités chimiques avec les phases silicatées) de l’hydrogène à haute pression, a contrario de plusieurs études précédentes. De ce fait, la différence entre les concentrations initiales élevées en eau que nous obtenons dans nos modèles d’accrétion et les concentrations en eau estimées sur Terre et sur Mars actuellement (2000 ppm et 200 ppm, respectivement) ne peut pas être expliquée par un réservoir d’hydrogène dans le noyau. Enfin, pour améliorer les modèles de formation du noyau, nous avons mis en évidence, par des modèles numériques, l’effet important de la viscosité de l’océan magmatique sur le taux d’équilibre entre noyaux et manteaux des planètes telluriques. Cela nous mène à ré-évaluer les modèles de formation des planètes telluriques basés sur des résultats expérimentaux à l’équilibre, notamment l’extension maximale de l’océan magmatique. L’évolution de la viscosité de l’océan magmatique a donc un impact important sur la composition finale des noyaux planétaires (par exemple les teneurs en soufre, oxygène ou silicium des noyaux terrestres et martiens)<br>The formation of the metallic planetary cores is a major event regarding to the evolution of physical and chemical properties of the telluric planets as we know it today. Indeed, the siderophile elements (i.e. which has affinities with metallic phases) abundances in planetary mantles is explained by the conditions of core-mantle segregation. Among these conditions, pressure, temperature and oxygen fugacity are the main ones controlling distribution of the elements between mantle and core. This distribution can only be explained by an equilibrium between metal and silicate obtained in a deep magma ocean, which implies high pressure and high temperature of equilibrium. Moreover, the oxygen fugacity must have varied during core-mantle segregation, in a reduced-to-oxidized path most probably. Another important parameter is whether or not water is present in the primordial magma ocean. Indeed, we now have more and more lines of evidences showing that the volatile elements, especially water, arrived during accretion and therefore during the core-mantle segregation, which means that water can have an effect on the latter phenomenon. Considering this hypothesis, we performed several high pressure-high temperature experiments which allowed us to model the formation of the core under hydrous conditions. These experiments demonstrated that water has a significant effect on the redox state evolution of planetary mantles. We use this redox evolution to constrain models of planetary accretions, based on a mix of EH and CI chondrites, showing a good agreement with models based on isotopic data. The output of these models is the maximum initial concentration in water on the Earth (1.2 -1.8 %wt) and on Mars (2.5-3.5 %wt). Furthermore, these experiments showed a lithophile behavior (i.e. which has affinities with silicated phases) of hydrogen at high pressures, contrary to previous studies. Therefore, the difference between high initial concentrations in water yielded by our accretion models and the estimated actual concentrations on the Earth and Mars (2000 ppm and 200 ppm, respectively) cannot be explained by a hydrogen reservoir in the core. Finally, to improve the models of core-mantle segregation, we showed by numerical simulations the important effect of the magma ocean viscosity on the equilibrium between planetary mantles and cores. it lead us to reevaluate the models of accretion based on experimental data, especially the maximum extent of magma oceans. The evolution of the magma ocean viscosity has therefore significant implications on the final composition of planetary cores (for instance on the sulfur, oxygen and silicon content of the Earth’s and Mars’ core)

Este trabalho é um estudo interdisciplinar envolvendo o cultivo de erva-cidreira (Melissa officinalis L.) e sua caracterização química. O objetivo deste estudo foi fornecer informação sobre a adubação orgânica e convencional, a sazonalidade e os efeitos dos elementos traço na produção dos óleos voláteis de Melissa officinalis. O modelo experimental utilizado foi em canteiros com delineamento inteiramente casualizados (DIC) com quatro repetições. Melissa officinalis foi submetida a diferentes sistemas de adubação e época de colheita. A concentração elementar foi determinada pela análise por ativação neutrônica instrumental (INAA), espectrometria de absorção atômica por forno de grafite (GF AAS) e espectrometria de emissão óptica com fonte de plasma indutivamente acoplado (ICP-OES) nas folhas de Melissa officinalis e nos solos de cultivo. Os óleos voláteis de Melissa officinalis foram extraídos pela técnica de hidrodestilação, utilizando-se o aparelho de Clevenger e os principais metabólitos secundários (citronelal, neral, geranial, citronelol, nerol e geraniol) foram determinados por cromatografia gasosa acoplada ao espectrômetro de massas (GC-MS). Primavera e verão apresentaram os óleos de melhor qualidade por possuírem menores teores de citronelol, nerol e geraniol. A formação de neral e geranial foi favorecida no manejo convencional correlacionado com a presença dos elementos Co, Cr, Mg e Ni presentes no solo, enquanto que a formação do citronelal foi favorecida no manejo orgânico correlacionado com o elemento Mn presente nas folhas de Melissa officinalis.<br>This work is an interdisciplinary study of Lemon balm cultivation (Melissa officinalis L.) and its chemical characterization. The objective of this study was to provide information about organic and mineral fertilization, season and trace elements effects on volatile oil production by the species Melissa officinalis. The experimental design was completely randomized with four replications. Melissa officinalis was under different fertilization and harvest season. Instrumental neutron activation analysis (INAA), graphite furnace atomic absorption spectrometry (GF AAS) and inductively coupled plasma optical emission spectrometry (ICP-OES) were applied to determine the elemental concentration in the soil and plant samples. The volatile oil was extracted by hydrodistillation and the compounds citronelal, neral, geranial, citronelol, nerol and geraniol were analyzed by gas chromatography coupled to a mass spectrometer (GC-MS). The best quality of the oil was obtained in spring and summer because the lower content of citronellol, nerol and geraniol. Neral and geranial formation was favored in the conventional management correlated with the presence of Co, Cr, Mg and Ni elements present in the soil, whereas citronellal formation was favored in organic management correlated with Mn element present in the Melissa officinalis leaves.

This thesis presents an investigation into a novel group of GaAs charge storage devices. These devices, which are an integration of bipolar and junction field effect transistor structures were conceived, designed, fabricated, and tested within this study. The purpose was to analyse new types of charge storage devices, which are suitable for fabrication and lead to the development of dynamic and nonvolatile memories in III-V compound semiconductors. Currently, III-V semiconductor storage devices consist only of capacitors, where data is destroyed during reading and electrical erasure is difficult. In this work, four devices types were demonstrated that exhibit nondestructive reading, and three of the prototypes can be electrically erased. All types use the junction field effect transistor (JFET) for charge sensing, with each having different bipolar or epitaxial layer structure controlling the junction gate. The bottom epitaxial layer in each case served as the JFET channel. Two of the device types have three alternately doped layers, while the remaining two have four alternately doped layers. In all cases, removal of majority carriers from the middle layers constitutes stored charge. The missing carriers deplete the current carrying a region of the JFET channel. Drain current of the JFET becomes an indicator of stored charge. The basic function of each JFET memory element type is independent of interchanging n- and p- type doping within the structure type. Some performance advantage can be realized, however, by sensing with an n-type channel as compared to p- type due to increased carrier mobility. All device types exhibit storage time characteristics of order ten seconds. Devices are constructed in epitaxial layers grown by molecular beam epitaxy (MBE) reactors. The design of the epitaxial layers is an intrinsic part, together with the electrical design, of the storage device concept. These concepts are implemented first with photolithography masks which are used in device fabrication. The fabrication methods employ wet chemical etching and ohmic metal liftoff techniques. Electrical dc and charge retention time characteristics along with functionality read/write operations for the memory element group are measured using commercial electronic test equipment.

Les laves alcalines sous-saturées riches en éléments volatils sont les marqueurs du rôle important des fluides dans le manteau et des interactions fluide-roche et magma-roche, processus clés pour comprendre la dynamique du manteau convectif et les interactions asthénosphère-lithosphère en domaine intracontinental. L’objectif de cette thèse est d’apporter de nouvelles contraintes sur la genèse des magmas alcalins en caractérisant les conditions de cristallisation, la source et les processus de fusion partielle à l’origine des néphélinites à olivine, des néphélinites à pyroxène et des basanites du champ volcanique du Jbel Saghro dans l’Anti-Atlas marocain. L’étude pétrologique et géochimique des roches et des minéraux, couplée à l’analyse des inclusions fluides a permis de contraindre les conditions pré-éruptives des néphélinites de Saghro à 1.7–2.2 GPa et ~1350 °C. Les minéraux montrent que les magmas néphélinitiques sont riches en éléments volatils (Cl, F, S), et les inclusions fluides indiquent que les magmas étaient saturés en fluide riche en CO2 à des pressions &gt; 590 MPa. Les différents assemblages minéralogiques des néphélinites et la présence de xénolites péridotitiques suggèrent une ascension rapide des néphélinites à olivine et des processus plus complexes en profondeur pour les néphélinites à pyroxène. La modélisation des processus de cristallisation fractionnée et de fusion partielle des laves mafiques de Saghro a permis de déterminer qu’elles sont issues de faibles taux de fusion partielle (0.6–2.5 %) d’une péridotite carbonatée enrichie en éléments incompatibles, au niveau de la transition grenat–spinelle (~80–85 km) et en présence d’amphibole. Les néphélinites de Saghro montrent une évolution temporelle avec une légère augmentation du taux de fusion et une diminution de la quantité d’amphibole au résidu des plus anciennes (néphélinites à olivine, 9.6 Ma) aux plus récentes (néphélinites à pyroxène, 2.9 Ma). Les basanites forment un système indépendant des néphélinites et sont issues de taux de fusion plus élevés. Les fortes variations dans leur composition chimique suggèrent qu’elles ont subi de la cristallisation fractionnée lors de leur ascension. Les caractéristiques particulières des néphélinites et basanites de Saghro (enrichissement en éléments incompatibles, anomalies négatives en K, Zr, Hf et Ti, rapports Ca/Al et Zr/Hf élevés) indiquent que leur source a subi un métasomatisme principalement carbonatitique. L’influence de ce métasomatisme est plus forte pour les néphélinites à pyroxène que pour les néphélinites à olivine, impliquant une évolution temporelle de l’intensité du métasomatisme. Ces résultats suggèrent des interactions fluide-roche sous le craton Nord-Ouest Africain, entraînant la formation d'un manteau métasomatisé par des composants carbonatitiques riches en CO2 au niveau de la transition lithosphère-asthénosphère. L’origine du métasomatisme provoquant l’enrichissement de la source et la formation de veines d’amphibole pourrait être liée à la fusion de reliquats de croûte océanique subductée. Les températures de fusion relativement faibles (&lt; 1350 °C) suggèrent l’absence d’anomalie thermique sous le Jbel Saghro, et favorisent donc un modèle de délamination de la lithosphère comme initiateur du volcanisme. Cependant, l’augmentation du taux de fusion partielle au cours du temps, également observée dans le Moyen Atlas, et les similitudes isotopiques et géochimiques avec les laves alcalines des îles Canaries ne permettent pas d’exclure une influence du panache des Canaries sur la source du volcanisme alcalin du Jbel Saghro<br>Volatile-rich, silica-undersaturated alkaline lavas record the important role of fluids during fluid-rock and magma-rock interactions in the mantle, which are key processes to understand the dynamics of the convective mantle and lithosphere-asthenosphere interactions in intracontinental settings. The aim of this thesis is to bring new constraints on the genesis of alkaline magmas by characterizing the crystallization conditions, the source and the partial melting processes taking part in the genesis of olivine nephelinites, pyroxene nephelinites and basanites from the Jbel Saghro volcanic field in the Moroccan Anti Atlas. The petrological and geochemical study of rocks and minerals coupled with the analysis of fluid inclusions constrains the pre-eruptive conditions of Saghro nephelinites to 1.7–2.2 GPa and ~1350 °C. Minerals show that nephelinitic magmas are rich in volatile elements (Cl, F, S), and fluid inclusions indicate that magmas were saturated with a CO2-rich fluid at pressures &gt; 590 MPa. The various mineralogical assemblages and the presence of peridotite xenoliths suggest a rapid ascent for olivine nephelinites and more complex processes at depth for pyroxene nephelinites. Fractional crystallization and partial melting modelling of Saghro mafic lavas indicate that they are low-degree melts (0.6–2.5 %) of an amphibole-bearing carbonated peridotite enriched in incompatible elements, at the garnet-spinel transition (~80–85 km). Saghro nephelinites display a temporal evolution with a slight increase of the degree of melting and a decrease of the amount of residual amphibole from the oldest (olivine nephelinites, 9.6 Ma) to the most recent (pyroxene nephelinites, 2.9 Ma). Basanites form a system that is independent from nephelinites and are slightly higher-degree melts. Important variations in their chemical composition suggest variable amounts of fractional crystallization during ascent. The peculiar characteristics of Saghro nephelinites and basanites (enrichment in incompatible elements, negative anomalies in K, Zr, Hf and Ti, high Ca/Al and Zr/Hf ratios) indicate that their source was affected by carbonatitic metasomatism. The influence of this metasomatism is stronger for pyroxene nephelinites than for olivine nephelinites. These results suggest fluid-rock interactions beneath the Northwest African Craton, leading to the formation of a metasomatized mantle by CO2-rich carbonatitic components at the lithosphere-asthenosphere transition. The origin of the metasomatism inducing source enrichment and the formation of amphibole veins could be attributed to the melting of relict subducted oce anic lithosphere. The relatively low melting temperatures (&lt; 1350 °C) suggest the absence of a thermal anomaly beneath the Jbel Saghro, and thus support a lithosphere delamination model as precursor of Saghro volca0,3nism. However, the increasing degree of partial melting over time, also observed in the Middle Atlas, together with the isotopic and geochemical similarities with Canary Islands alkaline lavas does not allow us to discard the influence of a deviation of the Canary mantle plume beneath northwest Africa

La Terre s'est formée il y a 4,5 milliards d'années par accumulation de poussières, de roches et de gaz. La composition de ces matériaux primitifs est aujourd'hui enregistrée dans les météorites. Cependant, l'origine des éléments volatils présents dans l'atmosphère (e.g., H, C, N, O) reste incomprise. En combinant des approches expérimentales à l'étude d'échantillons naturels, je me suis intéressé aux objets célestes contenant les ingrédients nécessaires à la formation de l'atmosphère terrestre. Il s'agit principalement des éléments volatils contenus dans la matière organique des météorites et dans la glace des corps cométaires. Afin de reconstituer l'histoire de formation de la Terre et de son atmosphère, j'ai utilisé les gaz nobles (He, Ne, Ar, Kr, Xe) comme traceurs des processus physiques ayant eu lieu dans le Système Solaire jeune et sur la Terre primitive. Bien que les comètes aient significativement contribué à l'apport des gaz nobles lourds de l'atmosphère (~20%), la majorité des autres éléments volatils terrestres (incluant l'eau, le carbone et l'azote) aurait été apportée par des corps dits "chondritiques", similaires aux météorites. Une fois formée, l'atmosphère a évolué au cours des temps géologiques, conduisant à l'établissement des conditions environnementales propices au développement de la vie. Les processus majeurs ayant affecté la masse et la composition de l'atmosphère ancienne se reflètent dans l'évolution isotopique du Xe atmosphérique, de 4.5 Ga à ~2 Ga. Nous étudions la possibilité d'apporter des contraintes sur l'âge des matériaux organiques retrouvés dans les roches sédimentaires plus anciennes que 2 Ga, en utilisant la signature isotopique du Xe qu'ils ont piégé au moment de leur formation. Cette méthode pourrait avoir des implications vis-à-vis de l'âge présumé des plus anciennes traces de vie organique<br>The Earth formed some 4.5 Ga from the accumulation of dust, rocks and gas. The composition of these primitive materials is today recorded in meteorites. However, the origin of volatile elements within the atmosphere (e.g., H, C, N, O) remains poorly understood. By combining experimental approaches and the analysis of natural samples, I studied the composition of celestial objects comprising the ingredients required for the formation of the terrestrial atmosphere. These mainly correspond to volatile elements trapped in meteoritic organic materials and in the ice of cometary bodies. In order to better understand the timeline of Earth's formation and volatile accretion, I used noble gases (He, Ne, Ar, Kr, Xe) as tracers of the physical processes that occurred in the early Solar System and on primitive Earth. Whilst comets significantly contributed to the heavy noble gas budget of the terrestrial atmosphere (~20%), most of the other terrestrial volatile elements (including water, carbon and nitrogen) would have been supplied to Earth by chondrtitic bodies similar to meteorites. Once formed, the atmosphere evolved over geological periods of time, leading to the establishment of suitable environmental conditions for life to develop. The major processes that affected the mass and composition of the ancient atmosphere can be studied by investigating the isotopic evolution of atmospheric Xe, from 4.5 Ga to ~2 Ga. We investigate the possibility to bring constraints on the age of organic materials isolated from sedimentary ricks older than 2 Ga, using the isotopic signature of the Xe component that was trapped at the time of their formation. This method could have implications regarding the presumed age of the earliest remnants of organic life

Dans l’objectif d’évaluer le devenir de sédiments subduits variablement enrichis en soufre dans des conditions P-T (pression – température) correspondant au toit de la plaque sous un arc volcanique, des expériences de fusion et de cristallisation ont été réalisées en conditions hydratées en presse piston-cylindre(3 GPa ; 650 – 1000°C ; ƒO2 ~ NNO) sur des sédiments naturels (pélite et marne), non dopés en éléments en traces et variablement enrichis en soufre (0, 1 et 2 wt% Sin). Lors de la fusion du sédiment pélitique, des liquides trondhjémitiques à granitiques sont produits en équilibre avec un résidu composé de grenat +disthène ± phengite ± quartz + rutile. Lors de la fusion du sédiment marneux, des liquides granodioritiques sont produits en équilibre avec un résidu constitué de grenat ± épidote ± clinopyroxène ± disthène ± quartz +rutile. L’ajout de soufre dans le système pour une ƒO2 ~ NNO conduit à une précipitation de sulfures. La quantité de fer (Fe2+) disponible dans le système diminue fortement (augmentation du Mg#) et impactegrandement les relations de phases : le grenat, l’épidote et la phengite sont déstabilisées au profit des pyroxènes, de la biotite ou encore de l’amphibole. La distribution des éléments en traces dans le liquide silicaté par rapport au sédiment de départ est également très affectée pour les systèmes dopés en soufre(ex : fractionnement des terres rares). Nous proposons, à partir des données obtenues dans des xénolites mantelliques (Grenade, Petites Antilles) et lors de modélisations géochimiques, que la contribution dans lecoin mantellique de 1 à 3 % de liquides trondhjémitiques/granitiques issus de la fusion de sédiments pélitiques modérément enrichis en soufre (≤ 1 wt% Sin) peut expliquer la variabilité de composition des basaltes du sud de l’arc des Petites Antilles (Grenade et Grenadines)<br>The main issue of this study is to constrain the fate of subducted sediments variably enriched in sulphur for P-T (pressure – temperature) relevant for the slab at sub-arc depth. Using piston-cylinder apparatus, we performed melting and crystallisation experiments (3 GPa; 650 – 1000°C; ƒO2 ~ NNO) on natural, trace elementundoped and volatile-rich sediments (pelite and marlstone). Experiments were conducted with variable water (5 to 10 wt% H2Oin) and sulphur (0, 1 and 2 wt% Sin) contents. Silicate melts produced by the fluid-present melting of pelite range from trondhjemitic to granitic compositions, are broadly peraluminous and coexist with garnet + kyanite ± phengite ± quartz + rutile. Those produced by the fluid-present melting of marlstone are sodic (granodioritic composition), metaluminous to slightly peraluminous and coexist with garnet ± epidote ± clinopyroxene ± kyanite ± quartz + rutile. Sulphur addition at ƒO2 ~ NNO leads to sulphide precipitation. Thus, iron (Fe2+) contents decrease (Mg# increase) in the system and this strongly impacts phase relationships: garnet, epidote and phengite are consumed in favour of pyroxens, biotite and amphibole. Trace-element distribution between silicate melt and starting bulk for S-doped systems is largely impacted (e.g. rare earth elements fractionation). On the basis of data obtained in mantle xenoliths(Grenada, Lesser Antilles) and from geochemical modelisations, we are suggesting that a contribution in the mantle wedge of 1 to 3 % of trondhjemitic/granitic melts derived from pelitic sediments (≤ 1 wt% Sin) mayaccount for the composition of basalts in the southern part of Lesser Antilles (Grenada and Grenadines)

La cellule a enclumes de diamant a chauffage laser co#2 a permis l'etude de la solubilite de l'ar dans les liquides silicates sous pression (p). L'evolution de la solubilite d'ar avec p dans sio#2 et mg#2sio#4 fondues presente un comportement jamais observe auparavant : une augmentation a peu pres lineaire a basse p, mais au dela de 5 gpa, elle chute soudainement d'un ordre de grandeur. Celle-ci est interpretee comme le resultat d'une competition entre deux phenomenes ayant lieu simultanement avec l'augmentation de p : l'elevation de la fugacite d'ar qui provoque une augmentation de la solubilite (loi de henry) et la densification du liquide qui entraine une diminution de la place disponible pour les atomes d'ar. L'adaptation du modele de la porosite ionique et de la distribution log-lineaire nous a permis de prevoir la chute de la solubilite pour le xe vers 2 gpa et pour l'he vers 8-10 gpa. Ce resultat implique une evolution de l'incompatible des gaz rares avec la profondeur. La presse multienclumes a permis l'etude du systeme silicate (et oxyde)- carbonate dans des conditions mantelliques. Le carbonate stable sous pression est la magnesite. Le carbone reste un element tres incompatible : les liquides formes lors des fusions partielles ont une composition 60% en moles de carbonate. Ces experiences ont mis en evidence l'existence d'une solution solide partielle enstatite-magnesite, dont le minimum de magnesite dissoute est de 0. 6% en poids. L'olivine, la wadsleyite et (fe,mg)o, semblent egalement presenter une solution solide avec la magnesite tout aussi importante, meme lors des fusions partielles. Cette faible solution des carbonates dans les silicates et oxydes porte des consequences importantes dans le cycle interne du carbone, car la totalite du carbone estime etre contenu dans le manteau peut se trouver sous la forme de solution solide. La magnesite ne se trouverait sous la forme d'une phase separee que quand la concentration est superieure a 6%.

Thesis (Ph. D.)--University of Oregon, 2005.<br>Typescript. Includes vita and abstract. Includes bibliographical references (leaves 143-153). Also available for download via the World Wide Web; free to University of Oregon users.

Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-23T10:48:05Z No. of bitstreams: 0<br>Made available in DSpace on 2017-11-23T10:48:05Z (GMT). No. of bitstreams: 0<br>Este trabalho é um estudo interdisciplinar envolvendo o cultivo de erva-cidreira (Melissa officinalis L.) e sua caracterização química. O objetivo deste estudo foi fornecer informação sobre a adubação orgânica e convencional, a sazonalidade e os efeitos dos elementos traço na produção dos óleos voláteis de Melissa officinalis. O modelo experimental utilizado foi em canteiros com delineamento inteiramente casualizados (DIC) com quatro repetições. Melissa officinalis foi submetida a diferentes sistemas de adubação e época de colheita. A concentração elementar foi determinada pela análise por ativação neutrônica instrumental (INAA), espectrometria de absorção atômica por forno de grafite (GF AAS) e espectrometria de emissão óptica com fonte de plasma indutivamente acoplado (ICP-OES) nas folhas de Melissa officinalis e nos solos de cultivo. Os óleos voláteis de Melissa officinalis foram extraídos pela técnica de hidrodestilação, utilizando-se o aparelho de Clevenger e os principais metabólitos secundários (citronelal, neral, geranial, citronelol, nerol e geraniol) foram determinados por cromatografia gasosa acoplada ao espectrômetro de massas (GC-MS). Primavera e verão apresentaram os óleos de melhor qualidade por possuírem menores teores de citronelol, nerol e geraniol. A formação de neral e geranial foi favorecida no manejo convencional correlacionado com a presença dos elementos Co, Cr, Mg e Ni presentes no solo, enquanto que a formação do citronelal foi favorecida no manejo orgânico correlacionado com o elemento Mn presente nas folhas de Melissa officinalis.<br>Tese (Doutorado em Tecnologia Nuclear)<br>IPEN/T<br>Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

For widespread use of biochar in agriculture and horticulture, it must be ensured that application will neither adversely affect soil and plants, nor exceed legislated contaminant concentrations. The most relevant groups of contaminants in biochar are potentially toxic elements (PTEs), polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOC). In this thesis, the concentrations of these groups of contaminants were analysed in 90 different biochars produced by slow pyrolysis. Subsequently, the concentrations were compared to legislation/guideline threshold values and linked to production conditions. The risk these contaminants pose to plant growth was also assessed, to give recommendations on production of safe biochar. PTEs can neither be formed nor destroyed, which means their presence in biochar is predominantly determined by feedstock type. However, significant levels of Cr, Fe and Ni were introduced into biochar from the furnace steel, whilst PTEs with low boiling points, such as As, Cd and Zn, partially evaporated during pyrolysis. PTEs were not responsible for phytotoxic effects observed for PTE-rich biochars despite biochar’s exceedance of available and total PTE threshold values for soil and soil amendments. Although initial tests were promising, the risk that PTE-rich biochars as amendment for soil and growing media pose, needs further investigation. The PAH concentration in biochar was markedly reduced by increasing carrier gas flow rate, and the type of feedstock also influenced the PAH content. However, there was no clear dependence of pyrolysis temperature on PAH concentrations, which was attributed to PAHs being increasingly formed and evaporated at higher pyrolysis temperatures. Ultimately, condensation of pyrolysis vapours and deposition on biochar was identified as the main risk for biochar contamination with PAHs, as this resulted in elevated concentrations of high-risk, higher molecular weight PAHs. Weaknesses in the pyrolysis unit design, such as cold zones, resulted in elevated concentrations of VOCs, as well as PAHs, in biochar. Comparing concentrations and phytotoxic potential of both compound groups, it was concluded that observed toxic effects were much more likely caused by VOCs in biochars containing both contaminants. Overall, formation of VOCs and PAHs cannot be prevented, but their presence in biochar resulting from retention and deposition can be minimised.

Rhyolites of the Picabo volcanic field (10.4-6.6 Ma) of the Yellowstone hotspot in eastern Idaho are preserved as thick ignimbrites and lavas along the margins of the Snake River Plain. This study presents new O and Hf isotope data and U-Pb geochronology from individual zircons, O isotope data from major phenocrysts, whole rock Sr and Nd isotope data, whole rock geochemistry, and trace element and volatile analyses of quartz-hosted melt inclusions, which were used to characterize the evolution of rhyolite generation through the eruptive sequence. The chemical composition of the first eruption of the caldera complex, the Tuff of Arbon Valley, suggests magma generation through repeated magma injection into the crust, remelting, crystallization, mixing, and crustal assimilation. Subsequent eruptions have diverse and low δ18O signatures indicating rhyolite generation through the remelting of variably hydrothermally altered volcanics, followed by rapid batch assembly. This thesis includes co-authored material previously published.

Etudes methodologiques concernant l'analyse non destructive des fractions volatiles et des hydrocarbures liquides pieges dans les inclusions fluides par des methodes ponctuelles et non destructives comme la microspectrometrie infra-rouge et raman et la microfluorometrie, et d'autre part la mesure des changements de volume et de composition lors de surchauffes sous pression de confinement dans les inclusions de la fluorine. Les apports originaux des etudes d'inclusions fluides a la connaissance des circulations de fluides dans les bassins sedimentaires et pour la definition des conditions de depot des gites mineraux dans des contextes geologiques differents sont montres. Trois principaux types de solutions peuvent etre definis: les eaux connees de la diagenese faible a moyennement salines; les saumures d'origine diapirique; les solutions qui resultent d'un melange entre eaux connees et solutions hydrothermales

A l’ère du « big data » et de l’intelligence artificielle, les recherches pour trouver de nouvelles façons de stocker et traiter l’information se multiplient. Dans le domaine des mémoires non volatiles, cette émulation a conduit à l’émergence de nouveaux composants, dont les OxRAM (oxide-based resistive random access memories) auxquels nous nous sommes intéressés dans cette thèse. Il s’agit d’un empilement métal-oxyde-métal où la couche d’oxyde commute entre au moins deux états de résistance stables lorsqu’une tension est appliquée. Nos travaux ont porté sur l'étude électrique de dispositifs en croix, de dimensions submicroniques (500 x 500 nm2 ou 100 x 100 nm2) avec, comme oxyde diélectrique, le dioxyde d’hafnium HfO2 ou le dioxyde de titane TiO2. Pour l'élaboration des oxydes, nous avons mis en oeuvre le dépôt par jets moléculaires (ou MBE pour molecular beam epitaxy), technique très peu utilisée jusqu’ici dans la communauté des OxRAM. Cette technique d'ultravide permet d'obtenir des films très purs alors qu'avec l’ALD (pour atomic layer deposition), le précurseur employé induit une contamination en carbone, azote ou chlore. L'une des clés de l’optimisation des propriétés électriques se trouve dans le contrôle de la quantité et de la distribution des lacunes d’oxygène. A cet effet, nous avons exploré l’incorporation de divers éléments aux couches de HfO2 et TiO2. La microstructure et la composition des films d'oxyde ainsi dopés ont été analysées, puis les dispositifs OxRAM ont été fabriqués et leurs caractéristiques électriques (courant-tension) ont été étudiées. Pour les OxRAM à base de HfO2 (mettant en jeu un mécanisme filamentaire), nous avons tout d'abord optimisé l'élaboration de HfO2 par MBE. Nous avons obtenu des dispositifs dont les propriétés électriques se situent au niveau de l'état de l'art international, notamment pour la fenêtre mémoire. Grâce à la croissance par MBE, nous obtenons une plus petite tension de forming et une plus grande fenêtre mémoire que pour des composants similaires, que nous avons fabriqués à partir de films préparés par ALD. Nous suggérons un lien entre contaminants carbonés et largeur de la fenêtre mémoire. Par rapport à l'état de l'art, nos objectifs étaient d’abaisser les courants de fonctionnement et d’atténuer la variabilité entre nombreux cycles ainsi qu'entre composants. Nous avons pour cela examiné les effets de l'ajout dans HfO2 des éléments Al, La ou Ti (de quelques % jusqu'à 30 %), par co-dépôt avec Hf. Grâce à ces additions, nous parvenons à réduire le courant de reset, la tension de forming et la variabilité du courant de reset. De plus, les mesures XPS (pour X-ray photoelectron spectroscopy) montrent une augmentation du taux de lacunes dans les couches La-HfO2, Ti-HfO2 et Al-HfO2. Concernant les composants à base de TiO2 (impliquant des mécanismes de type interfacial à l'une des deux interfaces avec les électrodes, dite active), nos objectifs étaient de diminuer les courants de fonctionnement et d’augmenter le nombre d’états de résistance accessibles stables. A cette fin, nous avons privilégié, là aussi, des stratégies matériaux. Nous avons modifié l'interface active du dispositif en y incorporant des hétéroéléments (Ne, N et B) par implantation ionique. La teneur en lacunes d’oxygène a été analysée par XPS tandis que la mobilité des lacunes a été quantifiée via leur énergie d’activation de diffusion Ea. Afin de déterminer Ea, nous avons mis au point un protocole expérimental original. Ainsi, nous avons établi que l'azote, dopant de type p dans TiO2, accroît la mobilité des lacunes tandis que le bore, dopant de type n, l’entrave et le néon, inerte, n'a pas d'incidence. L'énergie d'activation est minimale (0,4 eV) pour une implantation en azote de 1018 ions/cm3. La mobilité des lacunes n'est cependant pas le seul paramètre à améliorer : le transport des électrons à travers la barrière Schottky TiO2/Pt joue également un rôle crucial. [...]<br>In the age of big data and artificial intelligence, researches to find new ways to process and store the information multiply. In the field of non-volatile memories, this emulation has led to the emergence of new components, such as OxRAM (for oxide-based random access memories) in which we have been interested in during this PhD. It is a metal-oxide-metal stack where the oxide layer is able to switch between at least two stable resistance states under an applied voltage. In this work, we have studied sub-micrometer cross-point devices (500 x 500 nm2 or 100 x 100 nm2) with hafnium dioxide (HfO2) or titanium dioxide (TiO2) as dielectric oxide. The oxides have been deposited by molecular beam epitaxy (MBE), a technique that has rarely been used so far in the OxRAM community. With this ultra-vide technique, we can obtain very pure films whereas with atomic layer deposition (ALD), precursors induce carbon, nitrogen or chlorine contaminations. For the electrical properties optimization, one of the keys is the concentration and distribution control of oxygen vacancies. Regarding that, we have explored the incorporation of various elements in HfO2 and TiO2 layers. The microstructure and the composition of these doped films have been analyzed, afterward OxRAM devices have been fabricated and their electrical characteristics (current-voltage) have been studied. For HfO2-based OxRAM (involving a filamentary mechanism), we have firstly optimized the MBE HfO2 deposition. The devices then obtained have electrical properties which are as good as those of the state-of-the-art components, in particular for the memory window. Moreover, these MBE deposited devices have a smaller forming voltage and a larger memory window than equivalent components that we have fabricated with ALD grown layers. So, we suggest a link between carbon impurities and memory width. In light of the state of the art, our objectives were to lower working currents and to reduce the variability between numerous cycles and between components too. To this end, we have examined the effects of adding Al, La or Ti elements in HfO2 (from few % to 30 %), by co-deposition with Hf. Thanks to these additions, we manage to decrease the reset current, the forming voltage and the variability of the reset current. Furthermore, X-ray photoelectron spectroscopy (XPS) measurements show an increase of vacancies amount in La-HfO2, Ti-HfO2 and Al-HfO2 layers. Concerning TiO2-based components (for which the mechanism is interfacial and takes place at one of the two electrode interfaces, said active), our goals were to diminish working currents and to augment the number of accessible stable resistance states. For this purpose, we have also focused on material strategies. We have modified the active interface by heteroelements ion implantation (Ne, N and B). The oxygen vacancies content has been analyzed by XPS while the vacancies mobility has been quantified via their activation energy diffusion Ea. In order to determine Ea, we have developed an original experimental protocol. In this way, we establish that nitrogen, which is a p-type dopant in TiO2, heightens the oxygen vacancies mobility, whereas boron, which is a n-dopant, hinders it and the neon, inert, does not have any effect on vacancies mobility. The activation energy is minimal (0.4 eV) for a nitrogen dose of 1018 ions/cm3. However, the oxygen vacancies mobility is not the only parameter that we have to improve: the electronic transport through the TiO2/Pt Schottky barrier plays also a crucial role. The results achieved during this PhD attest to the pertinence of the MBE utilization and of an analysis that combines ionic and electronic aspects in order to improve the resistive switching phenomenon understanding and the OxRAM performances

Une nouvelle méthode de haute précision pour analyser les isotopes de Sn à avec double-spike 117Sn-122Sn a été développée<br>A new high-precision isotope method for analyzing Sn using the 117Sn-122Sn double-spike technique was developed

This diploma thesis deasl with the chemical charakterization of wine from selected PIWI varieties. The theoretical part describes the general origin and reason for breeding PIWI varieties, a closer characterization of selected three PIWI varieties, Johaniter, Hibernal and Solaris. The next part is devoted to the description of analytical methods that were used to determine the chemical characteristics. The experimental part is developed to the determination of chemical characteristics, namely general characteristics such as alcohol, total phenols, phenolic substances, volatile substances and elemental composition. The results show that are differences between wines from selected PIWI varieties in therms of chemical composition. The most represented organic acid was in the range of 735,1-1286,2mg/l malic acid. This was followed by acetic in the range of 100-400mg/l. The antioxidant activity was determined in the range of 0,2988-0,9683 mmol/l of Trollox and content of total phenols 273,5-390,3mg/l. Of the phenolic substances, gallic acid was the most represented, ranging from 6,9-13,9mg/l. As another, abundant phenolic substances, catechin in the range of 1,6-6,0mg/l was detected. Of the determined elements, phosphorus in the range of 165,4-450,5mg/l was the most represented. Representatives of ethyl ester, ethyl acetate, decanoic acid ethyl acetate and hexanoic acid ethyl ester, were detected as the most abundant volatiles. From the measured data it was evident that wines from PIWI varieties different from standard varieties, especially in the profile of aromatic substances.

Understanding crystallisation in magma chambers is a key challenge for igneous petrology. It is particularly important to understand the origins of layering in peralkaline rocks, e.g. the kakortokite (nepheline syenite), Ilímaussaq Complex, S. Greenland, as these are commonly associated with high value multi-element economic deposits. The kakortokite is a spectacular example of macrorhythmic (>5 m) layering. Each unit consists of three layers comprising arfvedsonite-rich (sodic-amphibole) black kakortokite at the base, grading into eudialyte-rich (sodic-zirconosilicate) red kakortokite, then alkali feldspar- and nepheline-rich white kakortokite. Each unit is numbered -19 to +17 relative to a characteristic well-developed horizon (Unit 0), however there is little consensus on their development. This project applies a multidisciplinary approach through field observations combined with petrography, crystal size distributions (CSDs), mineral and whole rock chemistries on Units 0, -8 to -11 and a phonolite/micro-nephelinolite (“hybrid”) sequence that crosscuts the layered kakortokite. Textures and compositions are laterally consistent across outcrop and indicators of current activity are rare. CSDs indicate in situ crystallisation with gravitational settling as a minor process. Chemical discontinuities occur across unit boundaries. The layering developed through large-scale processes under exceptionally quiescent conditions. The discontinuities reflect open-system behaviour; units were formed by an influx of volatile-rich magma that initiated crystallisation in a bottom layer. Nucleation was initially suppressed by high volatile element concentrations, which decreased to allow for crystallisation of arfvedsonite, followed by eudialyte, then alkali feldspar and nepheline to form each tripartite unit. The chemistry of the hybrid indicates mixing between a primitive (sub-alkaline) magma and kakortokite. Thus injections of magmas of varying compositions occurred, indicating a complex plumbing system below current exposure. The lessons learned at Ilímaussaq, which is extremely well exposed and preserved, are relevant to understanding magma chamber dynamics in the more common instances of pervasively altered peralkaline rocks.

This diploma thesis researches coffee authenticity problematice, mainly focusing on the authenticity of geographic origin. In the theoretical part of this work, botanical classification is described as well as production technology and processes. The work also includes chemical composition of coffee, describing the major components and changes during production phases. It describes major production areas of the world, in terms of general description and brief history. Problematics with coffee fraud and its identification are also described. Theoretical part also includes general geological description of 17 studied coffee growing regions. Experimental part is devoted to trace amount analysis of selected elements and volatile compounds. The element analysis was conducted using mass spectrometry or optical emission spectrometry, volatile compounds were determined using gas chromatography combined with mass spectrometry detection. Results were statistically described and analyzed, resulting in several discrimination models based on geographic origin.

<p>The formation of planets begins with collisions of tiny, micron-sized, dust grains. These grains reside in structures known as protoplanetary disks, rotating disks consisting of gas and dust that encircle young protostars as a natural outcome of star formation. Although the processes of planet formation and evolution take place over millions and billions of years, in our limited view we can only see snapshots of the different stages. Many of the formative processes are difficult, if not impossible, to observe directly. However, evidence of these events exists in the chemical composition of the bulk material and surfaces of planets themselves, the gas and solid components of protoplanetary disks, and planetary debris such as asteroids and comets. This thesis utilizes modeling and observations of the carbon and nitrogen content of protoplanetary disks to shed light on key factors that control the formation and chemical composition of planets. In addition, this thesis advances techniques for the elemental analysis of planetary surfaces facilitating the detection of salts on the surface of Mars.</p> <p>Chapter 2 estimates the maximum potential destruction of solid, refractory carbon in protoplanetary disks in an effort to explain the lack of carbon found in meteorites and the bulk silicate Earth relative to the interstellar materials that seeded their formation. In a T-Tauri disk assuming uniform turbulence and passive heating from stellar photons destruction of refractory carbon sources via oxidation and UV photolysis is limited to the warm, photochemically-active disk surface layers. Exploration of distinct disk environments, considering non-idealized mass transport or enhanced disk heating due to active stellar mass accretion, is needed to explain the widespread lack of carbon in rocky solar-system bodies.</p> <p>Chapters 3 and 4 present spectral observations by the Atacama Large Millimeter/submillimeter Array (ALMA) of mature, 5-11 Myr-old, protoplanetary disks in the Upper Scorpius region that indicate diverging behavior of the key carbon and nitrogen species in the disk gas as disks evolve. Selective depletion of CO from the gas may cause disk gas masses to be underestimated if based on CO measurements alone and further investigation of additional gas tracers is warranted.</p> <p>Depletion of CO from the gas in the outer regions of disks observed by ALMA may be the result of sequestration of carbon into less volatile species such as CO₂ and CH₃OH. Chapter 5 explores the fate of CO₂ and CH₃OH ices entering the inner regions of protoplanetary disks. Carbon returns to CO in unshielded transparent regions of the inner disk surface, consistent with infrared observations, but carbon reservoirs in the disk midplane may be distinct depending on the efficiency of mass transport in the disk.</p> <p>Chapter 6 examines the abilities of the Laser-Induced Breakdown Spectroscopy (LIBS) instrument ChemCam on the Mars rover Curiosity in regards to the detection of salts. LIBS analysis of a set of prepared sample pellets containing decreasing concentrations of salt identifies elemental emission lines of Cl, C, and S that are sensitive to changes in chloride, carbonate, and sulfate salt concentrations, respectively, and provides detection limits for ChemCam measurements of these salts.</p>

For the realization of a programmable logic device, or indeed any nanoscale device, we need a reliable method to probe the magnetization direction of local domains. For this purpose we extend investigations on the previously discovered tunneling anisotropic magneto resistance effect (TAMR) by scaling the pillar size from 100 µm down to 260 nm. We start in chapter 4 with a theoretical description of the TAMR effect and show experimental data of miniaturized pillars in chapter 5. With such small TAMR probes we are able to locally sense the magnetization on the 100 nm scale. Sub-micron TAMR and anisotropic magneto resistance (AMR) measurements of sub-millimeter areas show that the behavior of macroscopic (Ga,Mn)As regions is not that of a true macrospin, but rather an ensemble average of the behavior of many nearly identical macrospins. This shows that the magnetic anisotropies of the local regions are consistent with the behavior extracted from macroscopic characterization. A fully electrically controllable read-write memory device out the ferromagnetic semiconductor (Ga,Mn)As is presented in chapter 6. The structure consists of four nanobars which are connected to a circular center region. The first part of the chapter describes the lithography realization of the device. We make use of the sub-micron TAMR probes to read-out the magnetization state of a 650 nm central disk. Four 200 nm wide nanobars are connected to the central disk and serve as source and drain of a spin-polarized current. With the spin-polarized current we are able to switch the magnetization of the central disk by means of current induced switching. Injecting polarized holes with a spin angular momentum into a magnetic region changes the magnetization direction of the region due to the p-d exchange interaction between localized Mn spins and itinerant holes. The magnetization of the central disk can be controlled fully electrically and it can serve as one bit memory element as part of a logic device. In chapter 7 we discuss the domain wall resistance in (Ga,Mn)As. At the transition from nanobars to central disk we are able to generate 90° and 180° domain walls and measure their resistance. The results presented from chapter 5 to 7 combined with the preexisting ultracompact (Ga,Mn)As-based memory cell of ref. [Papp 07c] are the building blocks needed to realize a fully functioning programmable logic device. The work of ref. [Papp 07c] makes use of lithographically engineered strain relaxation to produce a structure comprised of two nanobars with mutually orthogonal uniaxial easy axes, connected by a narrow constriction. Measurements showed that the resistance of the constriction depends on the relative orientation of the magnetization in the two bars. The programmable logic device consists of two central disks connected by a small constriction. The magnetization of the two central disks are used as the input bits and the constriction serves as the output during the logic operation. The concept is introduced in the end of chapter 6 and as an example for a logic operation an XOR gate is presented. The functionality of the programmable logic scheme presented here can be straightforwardly extended to produce multipurpose functional elements, where the given geometry can be used as various different computational elements depending on the number of input bits and the chosen electrical addressing. The realization of such a programmable logic device is shown in chapter 8, where we see that the constriction indeed can serve as a output of the logic operation because its resistance is dependent on the relative magnetization state of both disks. Contrary to ref. [Papp 07c], where the individual magnetic elements connected to the constriction only have two non-volatile magnetic states, each disk in our scheme connected to the constriction has four non-volatile magnetic states. Switching the magnetization of a central disk with an electrical current does not only change the TAMR read-out of the respective disk, it also changes the resistance of the constriction. The resistance polar plot of the constriction maps the relative magnetization states of the individual disks. The presented device design serves as an all-electrical, all-semiconductor logic element. It combines a memory cell and data processing in a single monolithic paradigm<br>Für die Realisierung eines programmierbaren Logikelements oder beliebiger nanometer großer Bauteile, brauchen wir eine verlässlige Methode, um die Magnetisierungsrichtung lokaler Domänen auzulesen. Dafür erweitern wir die Untersuchungen an TAMR (tunneling magneto resistance) Strukturen und skalieren die Fläche des Tunnelkontakts von 100 µm auf 260 nm. In Kapitel 4 geben wir zunächst eine theoretische Beschreibung des TAMR Effekts und zeigen darauf im folgenden Kapitel 5 experimentelle Daten der miniaturisierten Tunnelkontakte. Mit diesen TAMR-Kontakten ist es möglich die Magnetisierung lokal in einer Grössenordnung von 100 nm zu detektieren. Sub-micron TAMR-Messungen und anisotrope Magnetowiderstandmessungen (AMR) an sub-millimeter Gebieten zeigen, dass das Verhalten von makrokopischen (Ga,Mn)As nicht das eines Makrospins ist, sondern ein Ensembledurchschnitt von vielen fast identischen Makrospins. Dieses Ergebnis ist mit der makroskopischen Beschreibung der lokalen magnetischen Aniotropien konform.\\ Ein rein elektrisch kontrollierbares Read-Write Speicherelement aus dem ferromagnetischen Halbleiter (Ga,Mn)As wird in Kapitel 6 gezeigt. Das Element besteht aus vier 200 nm breiten Streifen, die mit einer kreisförmigen zentralen Disc verbunden sind. Der erste Teil des Kapitels beschreibt die einzelnen Lithographieschritte zur Herstellung des Elements. Zum Auslesen der Magnetisierungsrichtung der zentralen Disc mit einem Durchmesser von 650 nm verwenden wir einen miniaturisierten TAMR-Kontakt. Die 200 nm breiten Streifen dienen als Quelle eines spinpolarisierten Stromes in die zentrale Disc. Das Injezieren von polarisierten Löchern mit einem Spin-Drehimpuls in eine magnetische Region verändert die Magnetisierung der Region durch p-d Austauschwechselwirkung zwischen lokalisierten Mn-Spins und den Löchern. Die Magnetisierung der zentralen Disc kann rein elektrisch kontrolliert werden and als Bit eines Logikelementes verwendet werden. In Kapitel 7 untersuchen wir den Domänenwiderstand in (Ga,Mn)As. Am Übergang von den Streifen zur zentralen Disc ist es möglich 90°- und 180° Domänenwände zu erzeugen und deren Widerstand zu messen.\\ Die Ergebnisse von Kapitel 5 bis 7, kombiniert mit dem bereits existierenden Ergebnissen einer ultrakompakten (Ga,Mn)As-basierenden Speicherzelle von Ref. [Papp 07c], sind die Schlüsselelemente die man zur Realisierung eines programmierbaren Logikelements benötigt. Die Arbeit von Referenz [Papp 07c] nutzt Lithographie induzierte Deformationsrelaxation, um eine Struktur zu erzeugen, die aus zwei senkrechten Streifen besteht und durch eine Verengung verbunden sind. Der Widerstand dieser Verengung ist von der relativen Magnetisierungsorientierung der beiden Streifen abhängig. Das programmierbare Logikelement besteht aus zwei zentralen Discs, die mittels einer schmalen Verengung verbunden sind. Die Magnetisierung der beiden zentralen Discs dienen als Eingänge und die Verengung als Ausgang während der Logikoperation. Das Konzept wird am Ende des sechsten Kapitels eingeführt und als Beispiel für eine Logikoperation wird ein XOR-Gate präsentiert. Die Funktionalität des hier gezeigten programmierbaren Logikschemas kann Problemlos auf ein multifunktionales Element erweitert werden. Diese Geometrie kann abhängig von der Anzahl der Eingänge und der gewählten Adressierung für verschiedene Rechenelemente genutzt werden. \\ Die Realisierung eines programmierbaren Logikelements ist in Kapitel 8 gezeigt. Der Widerstand der Verengung hängt von der relativen Magnetisierungsrichtung der beiden zentralen Discs ab und wird als Ausgang während der Logikoperation verwendet. Im Gegensatz zu Referenz [Papp 07c], indem die einzelnen über die Verengung verbundenen magnetischen Elemente jeweils nur zwei nicht-flüchtige magnetische Zustände besitzen, hat jede zentrale Disc in unserem Schema vier nicht-flüchtige magnetische Zustände. Das Verändern der Magnetisierungsrichtung einer zentralen Disc durch einen elektrischen Strom kann durch den jeweiligen TAMR-Kontakt und durch die Widerstandänderung der Verengung gemessen werden. Der Widerstands-Fingerabdruck (resistance polar plot) der Verengung zeigt die verschiedenen relativen Magnetisierungszutände der zentralen Discs.\\ Das hier präsentierte Konzept dient als reines Halbleiter und rein-elektrisches Logikelement. Es kombiniert eine Speicherzelle und Datenverarbeitung in einem neuartigen monolithischen Bauelement

Abstract Isobaric (200 MPa) experiments have been performed to investigate the effects of H2O alone or in combination with P, S, F or Cl on the phase relations and elemental and oxygen isotopic partitioning between immiscible silicate melts in the systems Fe2SiO4-Fe3O4-KAlSi2O6-SiO2, Fe3O4-KAlSi2O6-SiO2 and Fe3O4-Fe2O3-KAlSi2O6-SiO2 +/- plagioclase (An50). Experiments were heated in a newly-designed rapid-quench internally-heated pressure vessel at 1075, 1150 or 1200 oC for 2 hours. Water alone or in combination with P, S, or F significantly increases the temperature and composition range of two-liquid fields at fO2= NNO and MH buffers. Water-induced suppression of liquidus temperatures, considered with the effects of pressure on two-liquid fields stability in silicate melts, suggests that liquid phase separation may occur in some volatile-rich silicate magmas at pressures up to 2GPa. Two-liquid partition coefficients for Fe, Si, P and S correlate well with the degree of polymerization of the SiO2-rich conjugate melts and the data can be applied to assess the involvement of liquid-phase separation in the genesis of coexisting volatile-rich magmas. The partitioning of trace concentrations of selected HFSE, REE and transition elements between immiscible experimental volatile-rich melts at 1200 oC, 200 MPa has been determined at QFM, NNO and MH oxygen buffers. Water generally increases the partitioning of HFSE, REE and transition elements into the Fe-rich melt. Water alone, or combined with P or S, produces nearly parallel partitioning trends for HFSE and REE. Absolute partitioning values of transition elements are strongly dependent on the network-modifier composition of the melt. 18O in experimental immiscible melts with H2O or H2O and P or S partitions preferentially into the felsic conjugate melt (δ18O felsic melt- δ18O mafic melt values range from 0.4 to 0.8 permil) consistent with observations in anhydrous immiscible silicate melts. The expansion of the P-T-X-fO2 stability ranges of two- or three-liquid fields observed in the experimental melts demonstrates that liquid-immiscibility may be an important process in the evolution of some volatile-rich natural magmas. The results support an immiscible petrogenetic origin for some iron-oxide dominated, Kiruna-type, ore-deposits.<br>Thesis (Ph.D, Geological Sciences & Geological Engineering) -- Queen's University, 2012-04-10 15:06:35.797