Studio del comportamento meccanico di smalti porcellanati per substrati metallici

Composite porcelain enamels are inorganic coatings for metallic components based on a special ceramic-vitreous matrix in which specific additives are randomly dispersed. The ceramic-vitreous matrix is made by a mixture of various raw materials and elements and in particular it is based on boron-silicate glass added with metal oxides(1) of titanium, zinc, tin, zirconia, alumina, ecc. These additions are often used to improve and enhance some important performances such as corrosion(2) and wear resistance, mechanical strength, fracture toughness and also aesthetic functions. The coating process, called enamelling, depends on the nature of the surface, but also on the kind of the used porcelain enamel. For metal sheets coatings two industrial processes are actually used: one based on a wet porcelain enamel and another based on a dry-silicone porcelain enamel. During the firing process, that is performed at about 870°C in the case of a steel substrate, the enamel raw material melts and interacts with the metal substrate so enabling the formation of a continuous varying structure. The interface domain between the substrate and the external layer is made of a complex material system where the ceramic vitreous and the metal constituents are mixed. In particular four main regions can be identified, (i) the pure metal region, (ii) the region where the metal constituents are dominant compared with the ceramic vitreous components, (iii) the region where the ceramic vitreous constituents are dominant compared with the metal ones, and the fourth region (iv) composed by the pure ceramic vitreous material. It has also to be noticed the presence of metallic dendrites that hinder the substrate and the external layer passing through the interphase region. Each region of the final composite structure plays a specific role: the metal substrate has mainly the structural function, the interphase region and the embedded dendrites guarantee the adhesion of the external vitreous layer to the substrate and the external vitreous layer is characterized by an high tribological, corrosion and thermal shock resistance. Such material, due to its internal composition, functionalization and architecture can be considered as a functionally graded composite material. The knowledge of the mechanical, tribological and chemical behavior of such composites is not well established and the research is still in progress. In particular the mechanical performances data about the composite coating are not jet established. In the present work the Residual Stresses, the Young modulus and the First Crack Failure of the composite porcelain enamel coating are studied. Due to the differences of the porcelain composite enamel and steel thermal properties the enamelled steel sheets have residual stresses: compressive residual stress acts on the coating and tensile residual stress acts on the steel sheet. The residual stresses estimation has been performed by measuring the curvature of rectangular one-side coated specimens. The Young modulus and the First Crack Failure (FCF) of the coating have been estimated by four point bending tests (3-7) monitored by means of the Acoustic Emission (AE) technique(5,6). In particular the AE information has been used to identify, during the bending tests, the displacement domain over which no coating failure occurs (Free Failure Zone, FFZ). In the FFZ domain, the Young modulus has been estimated according to ASTM D6272-02. The FCF has been calculated as the ratio between the displacement at the first crack of the coating and the coating thickness on the cracked side. The mechanical performances of the tested coated specimens have also been related and discussed to respective microstructure and surface characteristics by double entry charts.

Two fluid numerical model for coastal applications

Wave breaking is an important coastal process, influencing hydro-morphodynamic processes such as turbulence generation and wave energy dissipation, run-up on the beach and overtopping of coastal defence structures. During breaking, waves are complex mixtures of air and water (“white water”) whose properties affect velocity and pressure fields in the vicinity of the free surface and, depending on the breaker characteristics, different mechanisms for air entrainment are usually observed. Several laboratory experiments have been performed to investigate the role of air bubbles in the wave breaking process (Chanson & Cummings, 1994, among others) and in wave loading on vertical wall (Oumeraci et al., 2001; Peregrine et al., 2006, among others), showing that the air phase is not negligible since the turbulent energy dissipation involves air-water mixture. The recent advancement of numerical models has given valuable insights in the knowledge of wave transformation and interaction with coastal structures. Among these models, some solve the RANS equations coupled with a free-surface tracking algorithm and describe velocity, pressure, turbulence and vorticity fields (Lara et al. 2006 a-b, Clementi et al., 2007). The single-phase numerical model, in which the constitutive equations are solved only for the liquid phase, neglects effects induced by air movement and trapped air bubbles in water. Numerical approximations at the free surface may induce errors in predicting breaking point and wave height and moreover, entrapped air bubbles and water splash in air are not properly represented. The aim of the present thesis is to develop a new two-phase model called COBRAS2 (stands for Cornell Breaking waves And Structures 2 phases), that is the enhancement of the single-phase code COBRAS0, originally developed at Cornell University (Lin & Liu, 1998). In the first part of the work, both fluids are considered as incompressible, while the second part will treat air compressibility modelling. The mathematical formulation and the numerical resolution of the governing equations of COBRAS2 are derived and some model-experiment comparisons are shown. In particular, validation tests are performed in order to prove model stability and accuracy. The simulation of the rising of a large air bubble in an otherwise quiescent water pool reveals the model capability to reproduce the process physics in a realistic way. Analytical solutions for stationary and internal waves are compared with corresponding numerical results, in order to test processes involving wide range of density difference. Waves induced by dam-break in different scenarios (on dry and wet beds, as well as on a ramp) are studied, focusing on the role of air as the medium in which the water wave propagates and on the numerical representation of bubble dynamics. Simulations of solitary and regular waves, characterized by both spilling and plunging breakers, are analyzed with comparisons with experimental data and other numerical model in order to investigate air influence on wave breaking mechanisms and underline model capability and accuracy. Finally, modelling of air compressibility is included in the new developed model and is validated, revealing an accurate reproduction of processes. Some preliminary tests on wave impact on vertical walls are performed: since air flow modelling allows to have a more realistic reproduction of breaking wave propagation, the dependence of wave breaker shapes and aeration characteristics on impact pressure values is studied and, on the basis of a qualitative comparison with experimental observations, the numerical simulations achieve good results.

Application of comprehensive gas chromatography (GCxGC) to measurements of volatile organic species in ambient air

The focus of this thesis was the in-situ application of the new analytical technique "GCxGC" in both the marine and continental boundary layer, as well as in the free troposphere. Biogenic and anthropogenic VOCs were analysed and used to characterise local chemistry at the individual measurement sites. The first part of the thesis work was the characterisation of a new set of columns that was to be used later in the field. To simplify the identification, a time-of-flight mass spectrometer (TOF-MS) detector was coupled to the GCxGC. In the field the TOF-MS was substituted by a more robust and tractable flame ionisation detector (FID), which is more suitable for quantitative measurements. During the process, a variety of volatile organic compounds could be assigned to different environmental sources, e.g. plankton sources, eucalyptus forest or urban centers. In-situ measurements of biogenic and anthropogenic VOCs were conducted at the Meteorological Observatory Hohenpeissenberg (MOHP), Germany, applying a thermodesorption-GCxGC-FID system. The measured VOCs were compared to GC-MS measurements routinely conducted at the MOHP as well as to PTR-MS measurements. Furthermore, a compressed ambient air standard was measured from three different gas chromatographic instruments and the results were compared. With few exceptions, the in-situ, as well as the standard measurements, revealed good agreement between the individual instruments. Diurnal cycles were observed, with differing patterns for the biogenic and the anthropogenic compounds. The variability-lifetime relationship of compounds with atmospheric lifetimes from a few hours to a few days in presence of O3 and OH was examined. It revealed a weak but significant influence of chemistry on these short-lived VOCs at the site. The relationship was also used to estimate the average OH radical concentration during the campaign, which was compared to in-situ OH measurements (1.7 x 10^6 molecules/cm^3, 0.071 ppt) for the first time. The OH concentration ranging from 3.5 to 6.5 x 10^5 molecules/cm^3 (0.015 to 0.027 ppt) obtained with this method represents an approximation of the average OH concentration influencing the discussed VOCs from emission to measurement. Based on these findings, the average concentration of the nighttime NO3 radicals was estimated using the same approach and found to range from 2.2 to 5.0 x 10^8 molecules/cm^3 (9.2 to 21.0 ppt). During the MINATROC field campaign, in-situ ambient air measurements with the GCxGC-FID were conducted at Tenerife, Spain. Although the station is mainly situated in the free troposphere, local influences of anthropogenic and biogenic VOCs were observed. Due to a strong dust event originating from Western Africa it was possible to compare the mixing ratios during normal and elevated dust loading in the atmosphere. The mixing ratios during the dust event were found to be lower. However, this could not be attributed to heterogeneous reactions as there was a change in the wind direction from northwesterly to southeasterly during the dust event.

Charakterisierung von plasmafunktionalisierten Oberflächen mittels ToF-SIMS und multivariaten Analysemethoden

Die grundlegenden Prinzipien und Möglichkeiten der Oberflächencharakterisierung mittels ToF-SIMS (Flugzeit-Sekundärionen Massenspektrometrie) werden an ausgewählten Beispielen aus einem aktuell laufenden und vom BMBF geförderten Verbundforschungsprojekt (Fkz: 03N8022A) zum Thema Nanofunktionalisierung von Grenzflächen vorgestellt. Ein Schwerpunkt innerhalb des Projekts stellen die nichtgeschlossenen Schichtsysteme dar, die entweder über Domänenstrukturen oder einer definierten Einzelfunktionalisierung neuartige funktionelle Oberflächen bereitstellen. Mithilfe der sehr oberflächensensitiven ToF-SIMS Methode sowie der Möglichkeit einer graphischen Darstellung lateraler Molekülionenverteilungen auf funktionalisierten Oberflächen können Informationen über Struktur und Belegungsdichte der Funktionsschicht gewonnen werden. Die Kombination des ToF-SIMS Experimentes und eines multivariaten Algorithmus (partial least squares, PLS) liefert eine interessante Möglichkeit zur quantitativen und simultanen Bestimmung von Oberflächeneigenschaften (Element- und molekulare Konzentrationen sowie Kontaktwinkelwerte). Da das ToF-SIMS Spektrum einer plasmafunktionalisierten Oberfläche im Allgemeinen eine Vielzahl unterschiedlicher Fragmentsignale enthält, lässt eine einfache eindimensionale Korrelation (z.B. CF3 - Fragmentintensität ßà CF3-Konzentration) den größten Teil der im Spektrum prinzipiell enthaltenen Information unberücksichtigt. Aufgrund der großen Anzahl von atomaren und molekularen Signalen, die repräsentativ für die chemische Struktur der analysierten Oberflächen sind, ist es sinnvoll, diese Fülle von Informationen zur Quantifizierung der Oberflächeneigenschaften (Elementkonzentrationen, Kontaktwinkel etc.) zu verwenden. Zusätzlich ermöglicht diese Methode eine quantitative Bestimmung der Oberflächeneigenschaften auf nur µm-großen Bereichen. Das ist vorteilhaft für Untersuchungen chemisch strukturierter Oberflächen, da die Größe der Strukturierung für viele Anwendungen in einem Bereich von mehreren µm liegt. Anhand eines Beispieles aus dem biologisch-medizinischen Fachgebiet, soll der erfolgreiche Einsatz multivariater Modelle aufgezeigt werden. In diesem Experiment wurden menschlichen Bindegewebs- (Fibroblasten) und Pankreaszellen auf plasmafunktionalisiserten Oberflächen kultiviert, um die Beeinflussung der Funktionalisierung auf das Zellwachstum zu untersuchen. Die plasmabehandelten Oberflächen wurden durch die Verwendung von TEM-Gittern mit µm-großen Öffnungen chemisch strukturiert und das Wachstumsverhalten der Zellen beobachtet. Jedem dieser µm-großen Bereiche können mithilfe der multivariaten Modelle quantitative Größen zugeordnet werden (Konzentrationen und Kontaktwinkelwerte), die zur Interpretation des Wachstumsverhaltens der Zellen beitragen.

Immunoconiugati contenenti tossine vegetali o siRNA per la deplezione selettiva di cellule leucemiche. Preparazione, citotossicità e studi di mutagenesi sito-specifica.

CD33 is a myeloid cell surface marker absent on normal hematopoietic stem cells and normal tissues but present on leukemic blasts in 90% of adult and paediatric acute myeloid leukaemia (AML) cases. By virtue of its expression pattern and its ability to be rapidly internalized after antibody binding, CD33 has become an attractive target for new immunotherapeutic approaches to treat AML. In this study two immunoconjugates were constructed to contain a humanised single-chain fragment variable antibody (scFv) against CD33 in order to create new antibody-derived therapeutics for AML. The first immunoconjugate was developed to provide targeted delivery of siRNAs as death effectors into leukemic cells. To this purpose, a CD33-specific scFv, modified to include a Cys residue at its C-terminal end (scFvCD33-Cys), was coupled through a disulphide bridge to a nona-d-arginine (9R) peptide carrying a free Cys to the N-terminal. The scFvCD33-9R was able to completely bind siRNAs at a protein to nucleic acid ratio of about 10:1, as confirmed by electrophoretic gel mobility-shift assay. The conjugate was unable to efficiently transduce cytotoxic siRNA (siTox) into the human myeloid cell line U937. We observed slight reductions in cell viability, with a reduction of 25% in comparison to the control group only at high concentration of siTox (300 nM). The second immunoconjugate was constructed by coupling the scFvCD33-Cys to the type 1 ribosome inactivating protein Dianthin 30 (DIA30) through a chemical linking The resulting immunotoxin scFvCD33-DIA30 caused the rapid arrest of protein synthesis, inducing apoptosis and leading ultimately to cell death. In vitro dose-dependent cytotoxicity assays demonstrated that scFvCD33-DIA30 was specifically toxic to CD33-positive cell U937. The concentration needed to reach 50 % of maximum killing efficiency (EC50) was approximately 0.3 nM. The pronounced antigen-restricted cytotoxicity of this novel agent makes it a candidate for further evaluation of its therapeutic potential.

Synthese von komplexen Polymerarchitekturen durch die kontrollierte Polymerisation von Reaktivester-Monomeren

Im Rahmen dieser Arbeit wurden zunächst die Grundlagen der Reaktivester-Chemiernuntersucht. Hierfür wurden verschiedenste Reaktivester-Monomere synthetisiert undrnmittels kontrolliert radikalischer Polymerisation polymerisiert. Diese Polymerernkonnten mit engen Molekulargewichtsverteilungen und vorherbestimmbarenrnMolekulargewichten dargestellt werden. Die daraus erhaltenen Kenntnisse wurdenrnauf verschiedene Bereiche angewendet.rnZum einen wurden auflösbare Netzwerke dargestellt. Dazu wurde 2,3,5,6-Tetrafluor-rn1,4-phenyldiacrylat synthetisiert. Durch die Verwendung eines reaktiven Vernetzersrnwurden Gele hergestellt, die durch den Einfluss von Nukleophilen gezielt auflösbarrnsind.rnAußerdem wurden erstmalig Blockcopolymer-Strukturen aus Poly(ethylenglycol),rnOligo(p-benzamid)en (OPBA) und Reaktivester-Polymeren synthetisiert. Diernpolymeranaloge Umsetzung des Reaktivesterblocks sollte zu stimuli responsivenrnSystemen führen, die durch thermischen Einfluss den Volumenanspruch verändernrnund somit das Aggregationsverhalten der OPBA bestimmen sollten.rnEin weiterer Aspekt war die Synthese von orthogonal funktionalisierbarenrnBlockcopolymeren, die durch Kombination von ringöffnender Polymerisation vonrnLactonen und RAFT Polymerisation von Reaktivester-Monomeren dargestellt werdenrnsollten. So war es erstmals möglich Blockcopolymere zu synthetisieren, die diernEigenschaften aliphatischer Polyester besitzen und durch Reaktivester-Chemiernfunktionalisiert werden konnten. Desweiteren wurden auf dieser Basis orthogonalrnfunktionalisierbare Blockcopolymere dargestellt, an die polymeranalog Nukleophilernangebunden und per Click-Chemie Poly(ethylenglycol)-Seitenketten eingefügtrnwerden konnten. Durch die Möglichkeit, die reaktiven Gruppen unterschiedlichrnansprechen zu können, eröffnet sich ein weites Feld der Funktionalisierung, ohne diernBioabbaubarkeit der aliphatischen Polyester zu beeinflussen.

Aeolian geomorphodynamics in endorheic basins of the Mongolian Gobi Desert

Die vorliegende Arbeit ist im Zuge des DFG Projektes Spätpleistozäne, holozäne und aktuelle Geomorphodynamik in abflusslosen Becken der Mongolischen Gobi´´ entstanden. Das Arbeitsgebiet befindet sich in der südlichen Mongolei im nördlichen Teil der Wüste Gobi. Neben einigen Teilen der Sahara (Heintzenberg, 2009), beispielsweise das Bodélé Becken des nördlichen Tschads (z.B. Washington et al., 2006a; Todd et al., 2006; Warren et al., 2007) wird Zentralasien als ein Hauptliefergebiet für Partikel in die globale Zirkulation der Atmosphäre gesehen (Goudie, 2009). Hauptaugenmerk liegt hierbei besonders auf den abflusslosen Becken und deren Sedimentablagerungen. Die, der Deflation ausgesetzten Flächen der Seebecken, sind hauptsächliche Quelle für Partikel die sich in Form von Staub respektive Sand ausbreiten. Im Hinblick auf geomorphologische Landschaftsentwicklung wurde der Zusammenhang von Beckensedimenten zu Hangdepositionen numerisch simuliert. Ein von Grunert and Lehmkuhl (2004) publiziertes Model, angelehnt an Ideen von Pye (1995) wird damit in Betracht gezogen. Die vorliegenden Untersuchungen modellieren Verbreitungsmechanismen auf regionaler Ebene ausgehend von einer größeren Anzahl an einzelnen punktuellen Standorten. Diese sind repräsentativ für die einzelnen geomorphologischen Systemglieder mit möglicherweise einer Beteiligung am Budget aeolischer Geomorphodynamik. Die Bodenbedeckung durch das charakteristische Steinpflaster der Gobi - Region, sowie unter anderem Korngrößenverteilungen der Oberflächensedimente wurden untersucht. Des Weiteren diente eine zehnjährige Zeitreihe (Jan 1998 bis Dez 2007) meteorologischer Daten als Grundlage zur Analyse der Bedingungen für äolische Geomorphodynamik. Die Daten stammen von 32 staatlichen mongolischen Wetterstationen aus der Region und Teile davon wurden für die Simulationen verwendet. Zusätzlich wurden atmosphärische Messungen zur Untersuchung der atmosphärischen Stabilität und ihrer tageszeitlichen Variabilität mit Mess-Drachenaufstiegen vorgenommen. Die Feldbefunde und auch die Ergebnisse der Laboruntersuchungen sowie der Datensatz meteorologischer Parameter dienten als Eingangsparameter für die Modellierungen. Emissionsraten der einzelnen Standorte und die Partikelverteilung im 3D Windfeld wurden modelliert um die Konvektivität der Beckensedimente und Hangdepositionen zu simulieren. Im Falle hoher mechanischer Turbulenz der bodennahen Luftschicht (mit einhergehender hoher Wind Reibungsgeschwindigkeit), wurde generell eine neutrale Stabilität festgestellt und die Simulationen von Partikelemission sowie deren Ausbreitung und Deposition unter neutraler Stabilitätsbedingung berechnet. Die Berechnung der Partikelemission wurde auf der Grundlage eines sehr vereinfachten missionsmodells in Anlehnung an bestehende Untersuchungen (Laurent et al., 2006; Darmenova et al., 2009; Shao and Dong, 2006; Alfaro, 2008) durchgeführt. Sowohl 3D Windfeldkalkulationen als auch unterschiedliche Ausbreitungsszenarien äolischer Sedimente wurden mit dem kommerziellen Programm LASAT® (Lagrange-Simulation von Aerosol-Transport) realisiert. Diesem liegt ein Langargischer Algorithmus zugrunde, mittels dessen die Verbreitung einzelner Partikel im Windfeld mit statistischer Wahrscheinlichkeit berechnet wird. Über Sedimentationsparameter kann damit ein Ausbreitungsmodell der Beckensedimente in Hinblick auf die Gebirgsfußflächen und -hänge generiert werden. Ein weiterer Teil der Untersuchungen beschäftigt sich mit der geochemischen Zusammensetzung der Oberflächensedimente. Diese Proxy sollte dazu dienen die simulierten Ausbreitungsrichtungen der Partikel aus unterschiedlichen Quellregionen nach zu verfolgen. Im Falle der Mongolischen Gobi zeigte sich eine weitestgehende Homogenität der Minerale und chemischen Elemente in den Sedimenten. Laser Bebohrungen einzelner Sandkörner zeigten nur sehr leichte Unterschiede in Abhängigkeit der Quellregionen. Die Spektren der Minerale und untersuchten Elemente deuten auf graitische Zusammensetzungen hin. Die, im Untersuchungsgebiet weit verbreiteten Alkali-Granite (Jahn et al., 2009) zeigten sich als hauptverantwortlich für die Sedimentproduktion im Untersuchungsgebiet. Neben diesen Mineral- und Elementbestimmungen wurde die Leichtmineralfraktion auf die Charakteristik des Quarzes hin untersucht. Dazu wurden Quarzgehalt, Kristallisation und das Elektronen-Spin-Resonanz Signal des E’1 - Centers in Sauerstoff Fehlstellungen des SiO2 Gitters bestimmt. Die Untersuchungen sind mit dem Methodenvorschlag von Sun et al. (2007) durchgeführt worden und sind prinzipiell gut geeignet um Herkunftsanalysenrndurchzuführen. Eine signifikante Zuordnung der einzelnen Quellgebiete ist jedoch auch in dieser Proxy nicht zu finden gewesen.

Temporal dynamics of benthic assemblages along a gradient of ocean acidification at a CO2 vent’s system of the Ischia Island

Global warming and ocean acidification, due to rising atmospheric levels of CO2, represent an actual threat to terrestrial and marine environments. Since Industrial Revolution, in less of 250 years, pH of surface seawater decreased on average of 0.1 unit, and is expected to further decreases of approximately 0.3-0.4 units by the end of this century. Naturally acidified marine areas, such as CO2 vent systems at the Ischia Island, allow to study acclimatation and adaptation of individual species as well as the structure of communities, and ecosystems to OA. The main aim of this thesis was to study how hard bottom sublittoral benthic assemblages changed trough time along a pH gradient. For this purpose, the temporal dynamics of mature assemblages established on artificial substrates (volcanic tiles) over a 3 year- period were analysed. Our results revealed how composition and dynamics of the community were altered and highly simplified at different level of seawater acidification. In fact, extreme low values of pH (approximately 6.9), affected strongly the assemblages, reducing diversity both in terms of taxa and functional groups, respect to lower acidification levels (mean pH 7.8) and ambient conditions (8.1 unit). Temporal variation was observed in terms of species composition but not in functional groups. Variability was related to species belonging to the same functional group, suggesting the occurrence of functional redundancy. Therefore, the analysis of functional groups kept information on the structure, but lost information on species diversity and dynamics. Decreasing in ocean pH is only one of many future global changes that will occur at the end of this century (increase of ocean temperature, sea level rise, eutrophication etc.). The interaction between these factors and OA could exacerbate the community and ecosystem effects showed by this thesis.

Early last glacial maximum in the southern Central Andes reveals northward shift of the westerlies at similar to 39 ka

The latitudinal position of the southern westerlies has been suggested to be a key parameter for the climate on Earth. According to the general notion, the southern westerlies were shifted equatorward during the global Last Glacial Maximum (LGM: ~24–18 ka), resulting in reduced deep ocean ventilation, accumulation of old dissolved carbon, and low atmospheric CO2 concentrations. In order to test this notion, we applied surface exposure dating on moraines in the southern Central Andes, where glacial mass balances are particularly sensitive to changes in precipitation, i.e. to the latitudinal position of the westerlies. Our results provide robust evidence that the maximum glaciation occurred already at ~39 ka, significantly predating the global LGM. This questions the role of the westerlies for atmospheric CO2, and it highlights our limited understanding of the forcings of atmospheric circulation.

Sensitivity of atmospheric CO2 and climate to explosive volcanic eruptions

Impacts of low-latitude, explosive volcanic eruptions on climate and the carbon cycle are quantified by forcing a comprehensive, fully coupled carbon cycle-climate model with pulse-like stratospheric aerosol optical depth changes. The model represents the radiative and dynamical response of the climate system to volcanic eruptions and simulates a decrease of global and regional atmospheric surface temperature, regionally distinct changes in precipitation, a positive phase of the North Atlantic Oscillation, and a decrease in atmospheric CO2 after volcanic eruptions. The volcanic-induced cooling reduces overturning rates in tropical soils, which dominates over reduced litter input due to soil moisture decrease, resulting in higher land carbon inventories for several decades. The perturbation in the ocean carbon inventory changes sign from an initial weak carbon sink to a carbon source. Positive carbon and negative temperature anomalies in subsurface waters last up to several decades. The multi-decadal decrease in atmospheric CO2 yields a small additional radiative forcing that amplifies the cooling and perturbs the Earth System on longer time scales than the atmospheric residence time of volcanic aerosols. In addition, century-scale global warming simulations with and without volcanic eruptions over the historical period show that the ocean integrates volcanic radiative cooling and responds for different physical and biogeochemical parameters such as steric sea level or dissolved oxygen. Results from a suite of sensitivity simulations with different magnitudes of stratospheric aerosol optical depth changes and from global warming simulations show that the carbon cycle-climate sensitivity γ, expressed as change in atmospheric CO2 per unit change in global mean surface temperature, depends on the magnitude and temporal evolution of the perturbation, and time scale of interest. On decadal time scales, modeled γ is several times larger for a Pinatubo-like eruption than for the industrial period and for a high emission, 21st century scenario.

Polygonal cracks in the seasonal semi-translucent CO2 ice layer in Martian polar areas

In this paper, we use morphological and numerical methods to test the hypothesis that seasonally formed fracture patterns in the Martian polar regions result from the brittle failure of seasonal CO2 slab ice. The observations by the High Resolution Imaging Science Experiment (HiRISE) of polar regions of Mars show very narrow dark elongated linear patterns that are observed during some periods of time in spring, disappear in summer and re-appear again in the following spring. They are repeatedly formed in the same areas but they do not repeat the exact pattern from year to year. This leads to the conclusion that they are cracks formed in the seasonal ice layer. Some of models of seasonal surface processes rely on the existence of a transparent form of CO2 ice, so-called slab ice. For the creation of the observed cracks the ice is required to be a continuous media, not an agglomeration of relatively separate particles like a firn. The best explanation for our observations is a slab ice with relatively high transparency in the visible wavelength range. This transparency allows a solid state green-house effect to act underneath the ice sheet raising the pressure by sublimation from below. The trapped gas creates overpressure and the ice sheet breaks at some point creating the observed cracks. We show that the times when the cracks appear are in agreement with the model calculation, providing one more piece of evidence that CO2 slab ice covers polar areas in spring.

Long-term bonding to eroded dentin requires superficial bur preparation

This study aims to evaluate the influence of different surface preparation techniques on long-term bonding effectiveness to eroded dentin.

Translocation and potential neurological effects of fine and ultrafine particles a critical update

ABSTRACT: Particulate air pollution has been associated with respiratory and cardiovascular disease. Evidence for cardiovascular and neurodegenerative effects of ambient particles was reviewed as part of a workshop. The purpose of this critical update is to summarize the evidence presented for the mechanisms involved in the translocation of particles from the lung to other organs and to highlight the potential of particles to cause neurodegenerative effects.Fine and ultrafine particles, after deposition on the surfactant film at the air-liquid interface, are displaced by surface forces exerted on them by surfactant film and may then interact with primary target cells upon this displacement. Ultrafine and fine particles can then penetrate through the different tissue compartments of the lungs and eventually reach the capillaries and circulating cells or constituents, e.g. erythrocytes. These particles are then translocated by the circulation to other organs including the liver, the spleen, the kidneys, the heart and the brain, where they may be deposited. It remains to be shown by which mechanisms ultrafine particles penetrate through pulmonary tissue and enter capillaries. In addition to translocation of ultrafine particles through the tissue, fine and coarse particles may be phagocytized by macrophages and dendritic cells which may carry the particles to lymph nodes in the lung or to those closely associated with the lungs. There is the potential for neurodegenerative consequence of particle entry to the brain. Histological evidence of neurodegeneration has been reported in both canine and human brains exposed to high ambient PM levels, suggesting the potential for neurotoxic consequences of PM-CNS entry. PM mediated damage may be caused by the oxidative stress pathway. Thus, oxidative stress due to nutrition, age, genetics among others may increase the susceptibility for neurodegenerative diseases. The relationship between PM exposure and CNS degeneration can also be detected under controlled experimental conditions. Transgenic mice (Apo E -/-), known to have high base line levels of oxidative stress, were exposed by inhalation to well characterized, concentrated ambient air pollution. Morphometric analysis of the CNS indicated unequivocally that the brain is a critical target for PM exposure and implicated oxidative stress as a predisposing factor that links PM exposure and susceptibility to neurodegeneration.Together, these data present evidence for potential translocation of ambient particles on organs distant from the lung and the neurodegenerative consequences of exposure to air pollutants.

Local degradation of structural, mechanical, electrical and chemical properties of membrane electrode assembly in polymer electrolyte fuel cell

Polymer electrolyte fuel cell (PEMFC) is promising source of clean power in many applications ranging from portable electronics to automotive and land-based power generation. However, widespread commercialization of PEMFC is primarily challenged by degradation. The mechanisms of fuel cell degradation are not well understood. Even though the numbers of installed units around the world continue to increase and dominate the pre-markets, the present lifetime requirements for fuel cells cannot be guarantee, creating the need for a more comprehensive knowledge of material’s ageing mechanism. The objective of this project is to conduct experiments on membrane electrode assembly (MEA) components of PEMFC to study structural, mechanical, electrical and chemical changes during ageing and understanding failure/degradation mechanism. The first part of this project was devoted to surface roughness analysis on catalyst layer (CL) and gas diffusion layer (GDL) using surface mapping microscopy. This study was motivated by the need to have a quantitative understanding of the GDL and CL surface morphology at the submicron level to predict interfacial contact resistance. Nanoindentation studies using atomic force microscope (AFM) were introduced to investigate the effect of degradation on mechanical properties of CL. The elastic modulus was decreased by 45 % in end of life (EOL) CL as compare to beginning of life (BOL) CL. In another set of experiment, conductive AFM (cAFM) was used to probe the local electric current in CL. The conductivity drops by 62 % in EOL CL. The future task will include characterization of MEA degradation using Raman and Fourier transform infrared (FTIR) spectroscopy. Raman spectroscopy will help to detect degree of structural disorder in CL during degradation. FTIR will help to study the effect of CO in CL. XRD will be used to determine Pt particle size and its crystallinity. In-situ conductive AFM studies using electrochemical cell on CL to correlate its structure with oxygen reduction reaction (ORR) reactivity

Valgus Hip With High Antetorsion Causes Pain Through Posterior Extraarticular FAI

BACKGROUND: Valgus hips with increased antetorsion present with lack of external rotation and posterior hip pain that is aggravated with hip extension and external rotation. This may be the result of posterior femoroacetabular impingement (FAI). QUESTIONS/PURPOSES: We asked whether (1) the range of motion (ROM); (2) the location of anterior and posterior bony collision zones; and (3) the prevalence of extraarticular impingement differ between valgus hips with increased antetorsion compared with normal hips and hips with idiopathic FAI. METHODS: Surface models based on CT scan reconstructions of 13 valgus hips with increased antetorsion, 22 hips with FAI, and 27 normal hips were included. Validated three-dimensional collision detection software was used to quantify the simulated hip ROM and the location of impingement on the acetabular and the femoral sides. RESULTS: Hips with coxa valga and antetorsion showed decreased extension, external rotation, and adduction, whereas internal rotation in 90° of flexion was increased. Impingement zones were more anteroinferior on the femur and posteroinferior on the acetabular (pelvic) side; and the zones were more frequently extraarticular, posterior, or to a lesser degree anterior against the inferior iliac spine. We found a higher prevalence of extraarticular impingement for valgus hips with increased antetorsion. CONCLUSIONS: Valgus hips with increased antetorsion predispose to posterior extraarticular FAI and to a lesser degree anteroinferior spine impingement. LEVEL OF EVIDENCE: Level II, prognostic study. See Guidelines for Authors for a complete description of levels of evidence.