Size-dependent phase transitions in nanostructured zirconia-scandia solid solutions.

Size effects on phase stability and phase transitions in technologically relevant materials have received growing attention. Several works reported that metastable phases can be retained at room temperature in nanomaterials, these phases generally corresponding to the high-temperature polymorph of the same material in bulk state. Additionally, size-dependent shifts in solubility limits and/or in the transition temperatures for on heating or on cooling cycles have been observed. ZrO2-Sc2O3 (zirconia-scandia) solid solutions are known to exhibit very high oxygen ion conductivity provided their structure is composed of cubic and/or pseudocubic tetragonal phases. Unfortunately, for solid zirconia-scandia polycrystalline samples with typical micrometrical average crystal sizes, the high-conductivity cubic phase is only stable above 600°C. Depending on composition, three low-conductivity rhombo-hedral phases (β, γ and δ) are stable below 600°C down to room temperature, within the compositional range of interest for SOFCs. In previous investigations, we showed that the rhombohedral phases can be avoided in nanopowders with average crystallite size lower than 35 nm.

Surface layer formation in polymer melts and in solutions

In this work the surface layer formation in polymer melts and in polymer solutions have been investigated with the atomic force microscope (AFM). In polymer melts, the formation of an immobile surface layer results in a steric repulsion, which can be measured by the AFM. From former work it is know, that polydimethyl siloxane (PDMS) forms a stable surface layer for molecular weights above 12 kDa. In the present thesis, polyisoprene (PI) was investigated apart from PDMS, by a)measuring the steric surface interactions and b)measuring the surface slip in hydrodynamic experiments. If a polymer flows over a surface, the flow velocity at the surface is larger then zero. If case of a surface layer formation the flow plane changes to the top of the adsorbed layer and the surface slip is reduced to zero. By measuring the surface slip in hydrodynamic experiments, it is therefore possible to determine the presence of a stable surface layer. The results show no stable repulsion for PI and only a small decrease of the surface slip. This indicates that PI does not form a stable surface layer, but is only adsorbed weakly to the surface. Furthermore for 8 kDa PDMS the timescale of the formation of a surface layer was investigated by changing themaximal force the tip applied to the surface. With a repulsive force present, applying a higher force than 15 nN resulted in a destruction of the surface layer, indicated by attractive forces. Reducing the applied force below 15 nN then resulted in an increase of the repulsion to the former state during one minute, thus indicating that a surface layer can be formed within one minute even under the influence of continuous measurements. As a next step, mixtures of two PDMS homopolymers with different chain lengths have been investigated. The aim was to verify theoretical predictions that shorter chains should predominate at the surface due to their smaller loss in conformational entropy. The measurements where done in dependence of the volume fractions of short and long chain PMDS. The results confirmed the short chain dominance for all mixtures with less then 90 vol.% long chain PDMS. Surface layer formation in solution was investigated for superplasticizers which are industrially used as an additive to cement. They change the surface interaction between the cement grains from attractive to repulsive and the freshlymixed cement paste therefore becomes liquid. The aimin this part of the thesis was, to investigate cement particle interactions in a close to real environment. Therefore calcium silicate hydrate phases have been precipitated onto an AFM tip and onto a calcite crystal and the interaction between these surfaces have beenmeasured with and without addition of superplasticizers. The measurements confirmed the change from attraction to repulsion upon addition of superplasticizers. The repulsive steric interaction increased with the length of the sidechain of the superplasticizer, and the dependence of the range of the steric interactions on the sidechain length indicated that the sidechains are in a coiled conformation.

Stable N isotope composition of nitrate reflects N transformations during the passage of water through a montane rain forest in Ecuador

Knowledge of the fate of deposited N in the possibly N-limited, highly biodiverse north Andean forests is important because of the possible effects of N inputs on plant performance and species composition. We analyzed concentrations and fluxes of NO3 −–N, NH4 +–N and dissolved organic N (DON) in rainfall, throughfall, litter leachate, mineral soil solutions (0.15–0.30 m depths) and stream water in a montane forest in Ecuador during four consecutive quarters and used the natural 15N abundance in NO3 − during the passage of rain water through the ecosystem and bulk δ15N values in soil to detect N transformations. Depletion of 15N in NO3 − and increased NO3 −–N fluxes during the passage through the canopy and the organic layer indicated nitrification in these compartments. During leaching from the organic layer to mineral soil and stream, NO3 − concentrations progressively decreased and were enriched in 15N but did not reach the δ15N values of solid phase organic matter (δ15N = 5.6–6.7‰). This suggested a combination of nitrification and denitrification in mineral soil. In the wettest quarter, the δ15N value of NO3 − in litter leachate was smaller (δ15N = −1.58‰) than in the other quarters (δ15N = −9.38 ± SE 0.46‰) probably because of reduced mineralization and associated fractionation against 15N. Nitrogen isotope fractionation of NO3 − between litter leachate and stream water was smaller in the wettest period than in the other periods probably because of a higher rate of denitrification and continuous dilution by isotopically lighter NO3 −–N from throughfall and nitrification in the organic layer during the wettest period. The stable N isotope composition of NO3 − gave valuable indications of N transformations during the passage of water through the forest ecosystem from rainfall to the stream.

Stable isotopes, sedimentology and geochemical analyses of Middle Eocene to early Miocene sediments of ODP Site 177-1090

During Leg 177 of the Ocean Drilling Program (ODP), a well-preserved middle Eocene to lower Miocene sediment record was recovered at Site 1090 on the Agulhas Ridge in the Atlantic sector of the Southern Ocean. This new sediment record shows evidence of a hitherto unknown late Eocene opal pulse. Lithological variations, compositional data, mass-accumulation rates of biogenic and lithogenic sediment constituents, grain-size distributions, geochemistry, and clay mineralogy are used to gain insights into mid-Cenozoic environmental changes and to explore the circumstances of the late Eocene opal pulse in terms of reorganizations in ocean circulation. The base of the section is composed of middle Eocene nannofossil oozes mixed with red clays enriched in authigenic clinoptilolite and smectite, deposited at low sedimentation rates (LE 2 cm/ka). It indicates reduced terrigenous sediment input and moderate biological productivity during this preglacial warm climatic stage. The basal strata are overlain by an extended succession (100 m, 4 cm/ka) of biosiliceous oozes and muds, comprising the upper middle Eocene, the entire late Eocene, and the lowermost early Oligocene. The opal pulse occurred between 37.5 and 33.5 Ma and documents the development of upwelling cells along topographic highs, and the utilization of a marine nutrient- and silica reservoir established during the pre-late Eocene through enhanced submarine hydrothermal activity and the introduction of terrigenous solutions from chemical weathering on adjacent continents. This palaeoceanographic overturn probably was initiated through the onset of increased meridional ocean circulation, caused by the diversion of the Indian equatorial current to the south. The opal pulse was accompanied by increased influxes of terrigenous detritus from southern African sources (illite), mediated by enhanced ocean particle advection in response to modified ocean circulation. The opal pulse ended because of frontal shifts to the south around the Eocene/Oligocene boundary, possibly in response to the opening of the Drake Passage and the incipient establishment of the Antarctic Circumpolar Current. Condensed sediments and a hiatus within the early Oligocene part of the section possibly point to an invigoration of the deep-reaching Antarctic Circumpolar Current. The mid-Oligocene to lower Miocene section on long time scale exhibits less pronounced lithological variations than the older section and points to relatively stable palaeoceanographic conditions after the dramatic changes in the late Eocene to early Oligocene.

Stable carbon and oxygen isotope compositions of bulk rock samples analyzed from the Zumaia section

Astronomical tuning of sedimentary records to precise orbital solutions has led to unprecedented resolution in the geological time scale. However, the construction of a consistent astronomical time scale for the Paleocene is controversial due to uncertainties in the recognition of the exact number of 405-kyr eccentricity cycles and accurate correlation between key records. Here, we present a new Danian integrated stratigraphic framework using the land-based Zumaia and Sopelana hemipelagic sections from the Basque Basin and deep-sea records drilled during Ocean Drilling Program (ODP) Legs 198 (Shatsky Rise, North Pacific) and 208 (Walvis Ridge, South Atlantic) that solves previous discrepancies. The new coherent stratigraphy utilises composite images from ODP cores, a new whole-rock d13C isotope record at Zumaia and new magnetostratigraphic data from Sopelana. We consistently observe 11 405-kyr eccentricity cycles in all studied Danian successions. We achieve a robust correlation of bioevents and stable isotope events between all studied sections at the ~100-kyr short-eccentricity level, a prerequisite for paleoclimatic interpretations. Comparison with and subsequent tuning of the records to the latest orbital solution La2011 provides astronomically calibrated ages of 66.022 ± 0.040 Ma and 61.607 ± 0.040 Ma for the Cretaceous-Paleogene (K-Pg) and Danian-Selandian 105 (D-S) boundaries respectively. Low sedimentation rates appear common in all records in the mid-Danian interval, including conspicuous condensed intervals in the oceanic records that in the past have hampered the proper identification of cycles. The comprehensive interbasinal approach applied here reveals pitfalls in time scale construction, filtering techniques in particular, and indicates that some caution and scrutiny has to be applied when building orbital chronologies. Finally, the Zumaia section, already hosting the Selandian Global Boundary Stratotype Section and Point (GSSP), could serve as the global Danian unit stratotype in the future.

Bulk stable carbon and oxygen isotopes from ODP Site 1258, and Fe intensities from ODP Site 1262, and minimal tuning age model options for ODP Site 1258 and 1262

Timing is crucial to understanding the causes and consequences of events in Earth history. The calibration of geological time relies heavily on the accuracy of radioisotopic and astronomical dating. Uncertainties in the computations of Earth's orbital parameters and in radioisotopic dating have hampered the construction of a reliable astronomically calibrated time scale beyond 40 Ma. Attempts to construct a robust astronomically tuned time scale for the early Paleogene by integrating radioisotopic and astronomical dating are only partially consistent. Here, using the new La2010 and La2011 orbital solutions, we present the first accurate astronomically calibrated time scale for the early Paleogene (47-65 Ma) uniquely based on astronomical tuning and thus independent of the radioisotopic determination of the Fish Canyon standard. Comparison with geological data confirms the stability of the new La2011 solution back to ~54 Ma. Subsequent anchoring of floating chronologies to the La2011 solution using the very long eccentricity nodes provides an absolute age of 55.530 {plus minus} 0.05 Ma for the onset of the Paleocene/Eocene Thermal Maximum (PETM), 54.850 {plus minus} 0.05 Ma for the early Eocene ash -17, and 65.250 {plus minus} 0.06 Ma for the K/Pg boundary. The new astrochronology presented here indicates that the intercalibration and synchronization of U/Pb and 40Ar/39Ar radiometric geochronology is much more challenging than previously thought.

(Table 1) List of samples with carbonate mineralogy, stable isotope, and accessory-mineral information

Petrographic and stable-isotope (d13C, d18O) patterns of carbonates from the Logatchev Hydrothermal Field (LHF), the Gakkel Ridge (GR), and a Late Devonian outcrop from the Frankenwald (Germany) were compared in an attempt to understand the genesis of carbonate minerals in marine volcanic rocks. Specifically, were the carbonate samples from modern sea floor settings and the Devonian analog of hydrothermal origin, low-temperature abiogenic origin (as inferred for aragonite in serpentinites from elsewhere on the Mid-Atlantic Ridge), or biogenic origin? Aragonite is the most abundant carbonate mineral in serpentinites from the two modern spreading ridges and occurs within massive sulfides of the LHF. The precipitation and preservation of aragonite suggests high Mg2+ and sulfate concentrations in fluids. Values of d18OPDB as high as +5.3 per mill for serpentinite-hosted aragonite and as high as +4.2 per mill for sulfide-hosted aragonite are consistent with precipitation from cold seawater. Most of the corresponding d13C values indicate a marine carbon source, whereas d13C values for sulfide-hosted aragonite as high as +3.6 per mill may reflect residual carbon dioxide in the zone of methanogenesis. Calcite veins from the LHF, by contrast, have low d18OPDB (-20.0 per mill to -16.1 per mill) and d13C values (-5.8 per mill to -4.5 per mill), indicative of precipitation from hydrothermal solutions (~129°-186°C) dominated by magmatic CO2. Calcite formation was probably favored by fluid rock interactions at elevated temperatures, which tend to remove solutes that inhibit calcite precipitation in seawater (Mg2+ and sulfate). Devonian Frankenwald calcites show low d18O values, reflecting diagenetic and metamorphic overprinting. Values of d13C around 0 per mill for basalt-hosted calcite indicate seawater-derived inorganic carbon, whereas d13C values for serpentinite-hosted calcite agree with mantle-derived CO2 (for values as low as -6 per mill) with a contribution of amagmatic carbon (for values as low as -8.6 per mill), presumably methane. Secondary mineral phases from the LHF for which a biogenic origin appears feasible include dolomite dumbbells, clotted carbonate, and a network of iron- and silica-rich filaments.

A general stability criterion for switched linear systems having stable and unstable subsystems

We report conditions on a switching signal that guarantee that solutions of a switched linear systems converge asymptotically to zero. These conditions are apply to continuous, discrete-time and hybrid switched linear systems, both those having stable subsystems and mixtures of stable and unstable subsystems.

Accurate Parabolic Navier-Stokes solutions of the supersonic flow around and elliptic cone

Flows of relevance to new generation aerospace vehicles exist, which are weakly dependent on the streamwise direction and strongly dependent on the other two spatial directions, such as the flow around the (flattened) nose of the vehicle and the associated elliptic cone model. Exploiting these characteristics, a parabolic integration of the Navier-Stokes equations is more appropriate than solution of the full equations, resulting in the so-called Parabolic Navier-Stokes (PNS). This approach not only is the best candidate, in terms of computational efficiency and accuracy, for the computation of steady base flows with the appointed properties, but also permits performing instability analysis and laminar-turbulent transition studies a-posteriori to the base flow computation. This is to be contrasted with the alternative approach of using order-of-magnitude more expensive spatial Direct Numerical Simulations (DNS) for the description of the transition process. The PNS equations used here have been formulated for an arbitrary coordinate transformation and the spatial discretization is performed using a novel stable high-order finite-difference-based numerical scheme, ensuring the recovery of highly accurate solutions using modest computing resources. For verification purposes, the boundary layer solution around a circular cone at zero angle of attack is compared in the incompressible limit with theoretical profiles. Also, the recovered shock wave angle at supersonic conditions is compared with theoretical predictions in the same circular-base cone geometry. Finally, the entire flow field, including shock position and compressible boundary layer around a 2:1 elliptic cone is recovered at Mach numbers 3 and 4

A molecular level picture of the stabilization of A-DNA in mixed ethanol–water solutions

Advances in computer power, methodology, and empirical force fields now allow routine “stable” nanosecond-length molecular dynamics simulations of DNA in water. The accurate representation of environmental influences on structure remains a major, unresolved issue. In contrast to simulations of A-DNA in water (where an A-DNA to B-DNA transition is observed) and in pure ethanol (where disruption of the structure is observed), A-DNA in ≈85% ethanol solution remains in a canonical A-DNA geometry as expected. The stabilization of A-DNA by ethanol is likely due to disruption of the spine of hydration in the minor groove and the presence of ion-mediated interhelical bonds and extensive hydration across the major groove.

Solvent dependence of dynamic transitions in protein solutions

A transition as a function of increasing temperature from harmonic to anharmonic dynamics has been observed in globular proteins by using spectroscopic, scattering, and computer simulation techniques. We present here results of a dynamic neutron scattering analysis of the solvent dependence of the picosecond-time scale dynamic transition behavior of solutions of a simple single-subunit enzyme, xylanase. The protein is examined in powder form, in D2O, and in four two-component perdeuterated single-phase cryosolvents in which it is active and stable. The scattering profiles of the mixed solvent systems in the absence of protein are also determined. The general features of the dynamic transition behavior of the protein solutions follow those of the solvents. The dynamic transition in all of the mixed cryosolvent–protein systems is much more gradual than in pure D2O, consistent with a distribution of energy barriers. The differences between the dynamic behaviors of the various cryosolvent protein solutions themselves are remarkably small. The results are consistent with a picture in which the picosecond-time scale atomic dynamics respond strongly to melting of pure water solvent but are relatively invariant in cryosolvents of differing compositions and melting points.

A compact difference scheme for numerical solutions of second order dual-phase-lagging models of microscale heat transfer

Dual-phase-lagging (DPL) models constitute a family of non-Fourier models of heat conduction that allow for the presence of time lags in the heat flux and the temperature gradient. These lags may need to be considered when modeling microscale heat transfer, and thus DPL models have found application in the last years in a wide range of theoretical and technical heat transfer problems. Consequently, analytical solutions and methods for computing numerical approximations have been proposed for particular DPL models in different settings. In this work, a compact difference scheme for second order DPL models is developed, providing higher order precision than a previously proposed method. The scheme is shown to be unconditionally stable and convergent, and its accuracy is illustrated with numerical examples.