Understanding the Reaction Mechanism of Nanocomposite Thermites

Nanocomposite energetics are a relatively new class of materials that combine nanoscale fuels and oxidizers to allow for the rapid release of large amounts of energy. In thermite systems (metal fuel with metal oxide oxidizer), the use of nanomaterials has been illustrated to increase reactivity by multiple orders of magnitude as a result of the higher specific surface area and smaller diffusion length scales. However, the highly dynamic and nanoscale processes intrinsic to these materials, as well as heating rate dependencies, have limited our understanding of the underlying processes that control reaction and propagation. For my dissertation, I have employed a variety of experimental approaches that have allowed me to probe these processes at heating rates representative of free combustion with the goal of understanding the fundamental mechanisms. Dynamic transmission electron microscopy (DTEM) was used to study the in situ morphological change that occurs in nanocomposite thermite materials subjected to rapid (10^11 K/s) heating. Aluminum nanoparticle (Al-NP) aggregates were found to lose their nanostructure through coalescence in as little as 10 ns, which is much faster than any other timescale of combustion. Further study of nanoscale reaction with CuO determined that a condensed phase interfacial reaction could occur within 0.5-5 µs in a manner consistent with bulk reaction, which supports that this mechanism plays a dominant role in the overall reaction process. Ta nanocomposites were also studied to determine if a high melting point (3280 K) affects the loss of nanostructure and rate of reaction. The condensed phase reaction pathway was further explored using reactive multilayers sputter deposited onto thin Pt wires to allow for temperature jump (T-Jump) heating at rates of ~5x10^5 K/s. High speed video and a time of flight mass spectrometry (TOFMS) were used to observe ignition temperature and speciation as a function of bilayer thickness. The ignition process was modeled and a low activation energy for effective diffusivity was determined. T-Jump TOFMS along with constant volume combustion cell studies were also used to determine the effect of gas release in nanoparticle systems by comparing the reaction properties of CuO and Cu2O.

Riffe und fazielle Entwicklung der florigemma-Bank (Korallenoolith, Oxfordium) im Süntel und östlichen Wesergebirge (NW-Deutschland

During the Sedimentation of the platform carbonate deposits of the Korallenoolith Formation (middle Oxfordian to early Kimmeridgian) small buildups ofcorals formed in the Lower Saxony Basin. These bioconstructions are restricted to particular horizons (Untere Korallenbank,ßorigenuna-Bank Member etc.) and represent patch reefs and biostromes. In this study, the development of facies, fossil assemblages, spatial distribution of fossils, and reefs of the ßorigenuna-Bank Member (upper Middle Oxfordian) in the Süntel Mts and the eastern Wesergebirge Mts is described; the formation of reefs is discussed in detail. Twelve facies types are described and interpreted. They vary between high-energy deposits as well winnowed oolites and quiet-water lagoonal mudstones. Owing to the significance of biota, micro- and macrofossils are systematically described. The reefs are preserved in growth position, are characterized by numerous corresponding features and belong to a certain reef type. According to their size, shape and framework, they represent patch reefs, coral knobs (sensu James, 1983), coral thrombolite reefs (sensu Leinfelder et al., 1994) or “Klein- and Mitteldickichte” (sensu Laternser, 2001). Their growth fabric corresponds to the superstratal (dense) pillarstone (sensu Insalaco, 1998). As the top of the ßorigenuna-Bank displays an erosional unconformity (so-called Hauptdiskontinuität), the top of the reefs are erosionally capped. Their maximum height amounts to at least the maximum thickness of the ßorigenuna-Bank which does not exceed 4 metres. The diversity of coral fauna of the reefs is relatively low; a total of 13 species is recorded. The coral community is over- whelmingly dominated by the thin-branched ramose Thamnasteria dendroidea (Lamouroux) that forms aggregations of colonies (77?. dendroidea thickets). Leafy to platy Fungiastrea arachnoides (Parkinson) and Thamnasteria concinna (Goldfuss) occur subordinately, other species are only of minor importance. In a few cases, the reef-core consisting of Th. dendroidea thickets is laterally encrusted by platy F. arachnoides and Th. concinna colonies, and microbial carbonates. This zonation reflects probably a succession of different reef builders as a result of changing environmental conditions (allogenic succession). Moreover, some reefs are overlain by a biostrome made of large Solenopora jurassica nodules passing laterally in a nerinean bed. Mikrobial carbonates promoted reef growth and favoured the preservation of reef organismn in their growth position or in situ. They exhibit a platy, dendroid, or reticulate growth form or occur as downward-facing hemispheroids. According to their microstructure, they consist of a peloidal, clotted, or unstructured fabric (predominately layered and poorly structured thrombolite as well as clotted leiolite) (sensu Schmid, 1996). Abundant endo- and epibiontic organisms (bivalves, gastropods, echinoids, asteroids, ophiuroids, crabs etc) are linked to the reefs. With regard to their guild structure, the reefs represent occurrences at which only a few coral species serve as builder. Moreover, microbial carbonates contribute to both building and binding of the reefs. Additional binder as well as baffler are present, but not abundant. According to the species diversity, the dweller guild comprises by far the highest number of invertebrate taxa. The destroyer guild chiefly encompasses bivalves. The composition of the reef community was influenced by the habitat structure of the Th. dendroidea thickets. Owing to the increase in encrusting organisms and other inhabitants of the thickets, the locational factors changed, since light intensity and hydrodynamic energy level and combined parameters as oxygen supply declined in the crowded habitat. Therefore a characteristic succession of organisms is developed that depends on and responds to changing environmental conditions („community replacement sequence“). The succession allows the differentiation of different stages. It started after the cessation of the polyps with boring organisms and photoautotrophic micro-encrusters (calcareous algae, Lithocodium aggregatum). Following the death of these pioneer organisms, encrusting and adherent organisms (serpulids, „Terebella“ species, bryozoans, foraminifers, thecideidinids, sklerospongid and pharetronid sponges, terebratulids), small mobile organisms (limpets), and microbial induced carbonates developed. The final stage in the community replacement sequence gave rise to small cryptic habitats and organisms that belong to these caves (cryptobionts, coelobites). The habitat conditions especially favoured small non-rigid demosponges (“soft sponges”) that tolerate reduced water circulation. Reef rubble is negligible, so that the reefs are bordered by fossiliferous micritic limestone passing laterally in micritic limestone. Approximately 10% of the study area (outcropping florigemma-Bank) corresponds to reefal deposits whereas the remaining 90% encompass lagoonal inter-reefal deposits. The reef development is a good example for the interaction between reef growth, facies development and sea-level changes. It was initiated by a sea-level rise (transgression) and corresponding decrease in the hydrodynamic energy level. Colonization and reef growth took place on a coarse-grained Substrate composed of oncoids, larger foraminifers and bioclasts. Reef growth took place in a calm marine lagoonal setting. Increasing abundance of spherical coral morphs towards the Northeast (section Kessiehausen, northwestem Süntel Mts) reflects higher turbidity and a facies transition to coral occurrences of the ßorigenuna-Bank Member in the adjacent Deister Mts. The reef growth was neither influenced by stonns nor by input of siliciclastic deposits, and took place in short time - probably in only a thousand years under most probably mesotrophic conditions. The mass appearance of solenoporids and nerineids in the upper part of the ßorigenuna-Bank Member point to enhanced nutrient level as a result of regression. In addition, this scenario of fluctuations in nutrient availability seems to be responsible for the cessation of reef corals. The sea level fall reached its climax in the subaerial exposure and palaeokarst development of the florigemma-Bank. The reef building corals are typical pioneer species. The blade-like, flattened F. amchnoides colonies are characterized by their light porous calcium carbonate skeleton, which is a distinct advantage in soft bottom environment. Thus, they settled on soft bottom exposing the large parts of its surface to the incoming light. On the other hand, in response to their light requirements they were also able to settle shaded canopy structures or reef caves. Th. dendroidea is an opportunistic coral species in very shallow, well illuminated marine environment. Their thin and densely spaced branches led to a very high surface/volume ratio of the colonies that were capable to exploit incoming light due to their small thamasterioid calices characterized by “highly integrated polyps”. In addition, sideward coalescence of branches during colony growth led to a wave-resistant framework and favoured the authochthonous preservation of the reefs. Asexual reproduction by fragmented colonies promoted reef development as Th. dendroidea thickets laterally extend over the sea floor or new reefs have developed from broken fragments of parent colonies. Similar build ups with Th. dendroidea as a dominant or frequent reef building coral species are known from the Paris Basin and elsewhere from the Lower Saxony Basin (Kleiner Deister Mts). These buildups developed in well-illuminated shallow water and encompass coral reefs or coral thrombolite reefs. Intra- and inter-reef deposits vary between well-winnowed reef debris limestone and mudstones representing considerably calmer conditions. Solenoporid, nerineids and diceratides belong to the characteristic fossils of these occurrences. However, diceratides are missing in theflorigemma-Bank Member. Th. dendroidea differs in its colonization of low- to high-energy environment from recent ramose scleractinian corals (e.g., Acropora and Porites sp.). The latter are restricted to agitated water habitats creating coral thickets and carpets. According to the morphologic plasticity of Th. dendroidea, thick-branched colonies developed in a milieu of high water energy, whereas fragile, wide- and thin-branched colonies prevail in low-energy settings. Due to its relatively rapid growth, Th. dendroidea was able to keep pace with increased Sedimentation rates. 68 benthonic foraminiferan species/taxa have been recognized in thin sections. Agglutinated foraminifers (textulariids) predominate when compared with rotaliids and milioliids. Numerous species are restricted to a certain facies type or occur in higher population densities, in particular Everticyclammina sp., a larger agglutinated foraminifer that occurs in rock building amounts. Among the 25 reef dwelling foraminiferal species, a few were so far only known from Late Jurassic sponge reefs. Another striking feature is the frequency of adherent foraminiferal species. Fauna and flora, in particular dasycladaleans and agglutinated foraminifers, document palaeobiogeographic relationships to the Tethys and point to (sub)tropical conditions. Moreover, in Germany this foraminiferan assemblage is yet uncompared. In Southern Germany similar tethyan type assemblages are not present in strata as young as Middle Tithonian.

Evolution of mylonitic microfabrics (EMM), a computer application for educational purposes

`Evolution of mylonitic microfabrics' (EMM) is an interactive Filemaker Pro 3.0 application that documents a series of see-through deformation experiments on polycrystalline norcamphor. The application comprises computer animations, graphics and text explanations designed to give students and researchers insight into the interaction and dynamic nature of small-scale, mylonitic processes like intracrystalline glide, dynamic recrystallization and strain localization (microshearing). EMM shows how mylonitic steady state is achieved at different strain rates and temperatures. First, rotational mechanisms like glide-induced vorticity, subgrain rotation recrystallization and rigid-body rotation bring grains' crystal lattices into orientations that are favorable for intracrystalline glide. In a second stage, selective elimination of grains whose lattices are poorly oriented for glide involves grain boundary migration. This strengthens the texture. Temperature and strain rate affect both the relative activity of different strain accommodation mechanisms and the rate of microfabric change. Steady-state microfabrics are characterized by stable texture, grain size and shape-preferred orientations of grains and domains. This involves the cyclical generation and elimination of dynamically recrystallized grains and microshear zones.

Caractérisation et délimitation des sous-espèces de Gesneria viridiflora (Gesneriaceae) dans les Antilles

Une taxonomie révisée et une connaissance des limites d’espèces demeurent toujours importantes dans les points chauds en biodiversité comme les Antilles où de nombreuses espèces endémiques sont retrouvées. Des limites d’espèces divergentes impliquent un différent nombre d’espèces retrouvées dans un écosystème, ce qui peut exercer une influence sur les décisions prises face aux enjeux de conservation. Les genres Gesneria et Rhytidophyllum qui forment les principaux représentants de la famille des Gesneriaceae dans les Antilles comprennent plusieurs taxons aux limites d’espèces ambigües et quelques espèces qui ont des sous-espèces reconnues. C’est le cas de Gesneria viridiflora (Decne.) Kuntze qui comprend quatre sous-espèces géographiquement isolées et qui présentent des caractères végétatifs et reproducteurs similaires et variables. Une délimitation d’espèces approfondie de ce complexe d’espèce est effectuée ici à partir d’une approche de taxonomie intégrative considérant des données morphologiques, génétiques et bioclimatiques. Les données morphologiques quantitatives et qualitatives obtenues à partir de spécimens d’herbier sont utilisées pour délimiter des groupes morphologiques à l’aide d’une analyse en coordonnées principales. Ces groupes sont ensuite testés à l’aide de séquences d’ADN de quatre régions nucléaires en utilisant une méthode bayesienne basée sur la théorie de la coalescence. Finalement, les occurrences et les valeurs de variables de température et de précipitation qui y prévalent sont utilisées dans une analyse en composantes principales bioclimatique pour comparer les groupes délimités morphologiquement et génétiquement. Les résultats de l’analyse morphologique multivariée supportent la distinction entre les groupes formés par les sous-espèces actuellement reconnues de G. viridiflora. Les résultats, incluant des données génétiques, suggèrent une distinction jusqu’ici insoupçonnée des populations du Massif de la Hotte au sud-ouest d’Haïti qui sont génétiquement plus rapprochées des populations de Cuba que de celles d’Hispaniola. Bioclimatiquement, les groupes délimités par les analyses morphologiques et génétiques sont distincts. L’approche de taxonomie intégrative a permis de distinguer cinq espèces distinctes plutôt que les quatre sous-espèces acceptées jusqu’à aujourd’hui. Ces espèces sont : G. acrochordonanthe, G. quisqueyana, G. sintenisii, G. sylvicola et G. viridiflora. Une carte de distribution géographique, un tableau de la nouvelle taxonomie applicable et une clé d’identification des espèces sont présentés. La nouvelle taxonomie déterminée dans cette étude démontre un endémisme insoupçonné dans plusieurs régions du point chaud en biodiversité des Antilles et souligne l’importance d’investiguer les limites d’espèces dans les groupes diversifiés comprenant des taxons aux limites d’espèces incomprises.

Microfluidic Encapsulation of Pickering Oil Microdroplets into Alginate Microgels for Lipophilic Compound Delivery

Alginate microgels are widely used as delivery systems in food, cosmetics, and pharmaceutical industries for encapsulation and sustained release of hydrophilic compounds and cells. However, the encapsulation of lipophilic molecules inside these microgels remains a great challenge because of the complex oil-core matrix required. The present study describes an original two-step approach allowing the easy encapsulation of several oil microdroplets within alginate microgels. In the first step, stable oil microdroplets were formed by preparing an oil-in-water (O/W) Pickering emulsion. To stabilize this emulsion, we used two solid particles, namely the cotton cellulose nanocrystals (CNC) and calcium carbonate (CaCO3). It was observed that the surface of the oil microdroplets formed was totally covered by a CNC layer, whereas CaCO3 particles were adsorbed onto the cellulose layer. This solid CNC shell efficiently stabilized the oil microdroplets, preventing them from undesired coalescence. In the second step, oil microdroplets resulting from the Pickering emulsion were encapsulated within alginate microgels using microfluidics. Precisely, the outermost layer of oil microdroplets composed of CaCO3 particles was used to initiate alginate gelation inside the microfluidic device, following the internal gelation mode. The released Ca2+ ions induced the gel formation through physical cross-linking with alginate molecules. This innovative and easy to carry out two-step approach was successfully developed to fabricate monodisperse alginate microgels of 85 pm in diameter containing around 12 oil microdroplets of 15 mu m in diameter. These new oil-core alginate microgels represent an attractive system for encapsulation of lipophilic compounds such as vitamins, aroma compounds or anticancer drugs that could be applied in various domains including food, cosmetics, and medical applications.

Synthetic biology in droplet-based microfluidics

Droplet microfluidics is an active multidisciplinary area of research that evolved out of the larger field of microfluidics. It enables the user to handle, process and manipulate micrometer-sized emulsion droplets on a micro- fabricated platform. The capability to carry out a large number of individual experiments per unit time makes the droplet microfluidic technology an ideal high-throughput platform for analysis of biological and biochemical samples. The objective of this thesis was to use such a technology for designing systems with novel implications in the newly emerging field of synthetic biology. Chapter 4, the first results chapter, introduces a novel method of droplet coalescence using a flow-focusing capillary device. In Chapter 5, the development of a microfluidic platform for the fabrication of a cell-free micro-environment for site-specific gene manipulation and protein expression is described. Furthermore, a novel fluorescent reporter system which functions both in vivo and in vitro is introduced in this chapter. Chapter 6 covers the microfluidic fabrication of polymeric vesicles from poly(2-methyloxazoline-b-dimethylsiloxane-b-2-methyloxazoline) tri-block copolymer. The polymersome made from this polymer was used in the next Chapter for the study of a chimeric membrane protein called mRFP1-EstA∗. In Chapter 7, the application of microfluidics for the fabrication of synthetic biological membranes to recreate artificial cell- like chassis structures for reconstitution of a membrane-anchored protein is described.

Environmental scanning electron microscope imaging of vesicle systems

The structural characteristics of liposomes have been widely investigated and there is certainly a strong understanding of their morphological characteristics. Imaging of these systems, using techniques such as freeze-fracturing methods, transmission electron microscopy, and cryo-electron imaging, has allowed us to appreciate their bilayer structures and factors which can influence this. However, there are few methods which all us to study these systems in their natural hydrated state; commonly the liposomes are visualized after drying, staining, and/or fixation of the vesicles. Environmental Scanning Electron Microscopy (ESEM) offers the ability to image a liposome in its hydrated state without the need for prior sample preparation. Within our studies we were the first to use ESEM to study liposomes and niosomes and we have been able to dynamically follow the hydration of lipid films and changes in liposome suspensions as water condenses on to, or evaporates from, the sample in real time. This provides insight into the resistance of liposomes to coalescence during dehydration, thereby providing an alternative assay of liposome formulation and stability.

Avenues de synthèse d’un matériau magnétique multifonctionnel à des fins de catalyse hétérogène

La catalyse est à la base de la fabrication de médicaments, de produits textiles, d‘engrais, des pots d’échappement, et une multitude d’autres applications de notre quotidien. En effet, dans les pays industrialisés jusqu’à 80% des produits manufacturés utilisés au quotidien ont nécessité au moins une étape de catalyse lors de leur fabrication. Outre être actif, il est primordial pour un catalyseur performant d’être résistant à la désactivation qui se traduit par la perte d’activité ou de sélectivité d’un catalyseur au cours du temps. La synthèse d’un matériau multifonctionnel permet de répondre à ces différents critères. L’objectif d’un design intelligent de matériaux est de mener à des effets synergiques de chacune des composantes. Pour un catalyseur, en plus d’être actif et sélectif pour le produit désiré, il faut en plus qu’il soit durable, stable dans le temps, et permette d’être réutilisable. L’objectif de ce projet est de faire une synthèse originale, simple et reproductible d’un catalyseur actif et résistant à la désactivation. De base, un catalyseur se compose d’un support et d’un matériau actif. La nature, la morphologie et l’agencement de ces derniers dictent le comportement chimique du catalyseur final. Comme matériau actif, les nanoparticules d’or sont très prisées en raison de leur potentiel de catalyse élevée pour de nombreuses réactions. Cependant, aux températures de fonctionnement de la catalyse, les nanoparticules d’or ont tendance à se désactiver par coalescence. Pour remédier à cela, il est possible de déposer une couche de silice mésoporeuse afin de protéger les NPs d’or des rudes conditions de réaction tout en étant perméables aux espèces réactives. Plusieurs types de matériaux peuvent servir de support aux nanoparticules d’or. À ce titre, les particules d’oxydes de fer magnétiques telles que la magnétite (Fe[indice inférieur 3]O[indice inférieur 4]) sont intéressantes pour leur potentiel hyperthermique, phénomène par lequel des nanoparticules (NPs) magnétiques transforment de l’énergie électromagnétique provenant d’un champ externe haute fréquence en chaleur, créant ainsi des nano-fours. Une première couche de silice est utilisée comme matrice de greffage afin de fixer les nanoparticules d’or sur la magnétite. La structure visée est illustrée à la Figure ci-dessous. Figure 1 Structure du catalyseur de Fe2O4@SiO2-Au-SiO2m (Ge, Zhang, Zhang, & Yin, 2008) Plusieurs avenues d’assemblage et de synthèse sont explorées pour chacune des composantes de la structure visée. Les avantages et inconvénients ainsi que des mécanismes sont proposés pour chaque voie de synthèse. Le matériau est utilisé comme catalyseur pour la réaction de réduction du 4-Nitrophénol par du NaBH4. Pour ce qui est de la synthèse de magnétite par voie solvothermique, il a été démontré qu’il était important d’être dans un milieu sous pression puisque l’étape limitante de la réaction est la solubilité des particules de magnétites dans le milieu. Cela est en accord avec le principe de mûrissement d’Ostwald selon lequel les petites particules ont tendance à se dissoudre dans le milieu et précipiter à la surface des plus grosses particules de façon à diminuer l’énergie interfaciale. Cette synthèse a été reproduite avec succès et a mené à la production de nanoparticules de Fe[indice inférieur 3]O[indice inférieur 4] sphériques creuses d’une taille de 150 [plus ou moins] 30nm. Ces sphères creuses ont été recouvertes d’une couche de silice dense par une méthode de Stöber modifiée. Le recouvrement forme des amas de particules et est non uniforme en raison de la présence de poly(éthlyène glycol) à la sur face de la magnétite, un adjuvant présent lors de sa synthèse afin d’améliorer la dispersion de la magnétite. La synthèse et le greffage d’AuNPs sont bien maîtrisés : les AuNPs ont une taille de 17 [plus ou moins] 6nm et la quantité d’or greffé est assez élevée. Ultimement, une méthode de greffage alternative tel que le greffage par croissance in situ de nanoparticules d’or pourrait être emprunté afin d’obtenir des particules plus petites. Pour ce qui est de la formation d’une couche de silice mésoporeuse, la méthode par calcination est une meilleure option que par gravure chimique en raison de sa sélectivité envers la couche externe de silice plus élevée ainsi que la formation apparente de pores.