Studio del comportamento catalitico nella reazione di Water Gas Shift a media ed alta temperatura

Per massimizzare la quantità di H2 nel gas di sintesi ottenuto dal processo di Steam Reforming (SR) si utilizza la reazione di Water Gas Shift (WGS): CO + H2O ⇆ CO2 + H2 ∆H0298 = - 41,2 KJ/mol Sulla base di sistemi catalitici Cu/Zn/Al si è cercato di modificarne la composizione per ottenere catalizzatori attivi e stabili in un intervallo di temperatura tra 350-450 °C, (High Temperature Shift o HTS), al fine di sostituire i tradizionali sistemi a base di Fe/Cr, in relazione alle limitazioni ambientali all’utilizzo del Cr e per poter operare con valori inferiori del rapporto S/DG. Si sono inoltre studiate le caratteristiche dei catalizzatori e le condizioni di reazione che favoriscono la produzione di metilammine ed alcoli nel processo a temperature intermedie, tra 300-350 °C (Middle Temperature Shift o MTS), in relazione alla disattivazione che questi composti comportano nel processo di SR a seguito del riciclo della fase acquosa dal reattore di WGS.

La navigazione nella chirurgia oncologica ortopedica: Applicazione ed implementazione di nuove tecnologie per il trattamento chirurgico dei tumori dell'apparato muscolo-scheletrico, studio pilota

Nel presente progetto di ricerca, da novembre 2011 a novembre 2013 , sono stati trattati chirurgicamente, con l’assistenza del navigatore , pazienti con tumori ossei primitivi degli arti, del bacino e del sacro, analizzando i risultati degli esami istologici dei margini di resezione del tumore e i risultati clinici e radiografici. Materiali e metodi : Abbiamo analizzato 16 pazienti 9 maschi e 7 femmine , con un'età media di 31 anni (range 12-55 ). Di tutti i pazienti valutati 8 avevano una localizzazione agli arti inferiori , 4 al bacino e 4 all'osso sacro . Solo quelli con osteosarcoma parostale , Cordoma e Condrosarcoma non sono stati sottoposti a terapia antiblastica . Solo un paziente è stato sottoposto a radioterapia postoperatoria per una recidiva locale . Tutti gli altri pazienti non sono stati trattati con la radioterapia per l’ adeguatezza dei margini di resezione . Non ci sono state complicanze intraoperatorie . Nel periodo postoperatorio abbiamo osservato una vescica neurologica , una paresi sciatica, due casi di infezione di cui una superficiale e una profonda, tutti e quattro i pazienti con sarcoma sacrale sviluppati hanno avuto ritardato della guarigione della ferita e di questi tre hanno avuto incontinenza sfinterica. In tutti i casi si è ottenuta una eccellente risultato clinico e radiografico , con soddisfazione del paziente , corretto contatto tra l'osteotomia e l'impianto che apparivano stabili ai primi controlli ambulatoriali ( FU 19 mesi). Risultati: La chirurgia assistita da calcolatore ha permesso di migliorare l’esecuzione delle resezioni ossee prevista dal navigatore. Questa tecnologia è valida e utile per la cure dei tumori dell’apparato scheletrico, soprattutto nelle sedi anatomiche più complesse da trattare come la pelvi, il sacro e nelle resezioni intercalari difficoltose nell’ottenere un margine di resezione ampio e quindi di salvare l’articolazione e l’arto stesso.

Comportamento tribologico di materiali per componenti di interesse industriale: Failure analysis e prove tribologiche in laboratorio

L’attività di ricerca della presente tesi di dottorato ha riguardato sistemi tribologici complessi di interesse industriale per i quali sono stati individuati, mediante failure analysis, i meccanismi di usura dominanti. Per ciascuno di essi sono state studiate soluzioni migliorative sulla base di prove tribologiche di laboratorio. Nella realizzazione di maglie per macchine movimentazione terra sono ampiamente utilizzati i tradizionali acciai da bonifica. La possibilità di utilizzare i nuovi microlegati a medio tenore di carbonio, consentirebbe una notevole semplificazione del ciclo produttivo e benefici in termini di costi. Una parte della tesi ha riguardato lo studio del comportamento tribologico di tali acciai. E’ stato anche affrontato lo studio tribologico di motori idraulici, con l’obiettivo di riuscire a migliorarne la resistenza ad usura e quindi la vita utile. Sono state eseguite prove a banco, per valutare i principali meccanismi di usura, e prove di laboratorio atte a riprodurre le reali condizioni di utilizzo, valutando tecniche di modificazione superficiale che fossero in grado di ridurre l’usura dei componenti. Sono state analizzate diverse tipologie di rivestimenti Thermal Spray in termini di modalità di deposizione (AFS-APS) e di leghe metalliche depositate (Ni,Mo,Cu/Al). Si sono infine caratterizzati contatti tribologici nel settore del packaging, dove l’utilizzo di acciai inox austenitici è in alcuni casi obbligatorio. L’acciaio inossidabile AISI 316L è ampiamente utilizzato in applicazioni in cui siano richieste elevate resistenze alla corrosione, tuttavia la bassa resistenza all’usura, ne limitano l’impiego in campo tribologico. In tale ambito, è stata analizzata una problematica tribologica relativa a macchine automatiche per il dosaggio di polveri farmaceutiche. Sono state studiate soluzioni alternative che hanno previsto sia la completa sostituzione dei materiali della coppia tribologica, sia l’individuazione di tecniche di modificazione superficiale innovative quali la cementazione a bassa temperatura anche seguita dalla deposizione di un rivestimento di carbonio amorfo idrogenato a-C:H

Influence of defects and disorder on anomalous Hall effect and spin Seebeck effect on permalloy and Heusler compounds

In dieser Arbeit wurden dünne Schichten von Heusler-Verbindungen hergestellt und auf ihre Transporteigenschaften hin untersucht.rnDer Anomale Hall-Effekt (AHE) ist dabei von besonderem Interesse. Er ist ein seit langer Zeit bekannter, jedoch noch nicht vollständig verstandener Transport-Effekt. Die meisten Veröffentlichungen theoretischer Arbeiten konzentrieren sich auf den Einfluss eines bestimmten Beitrags zum AHE. Tatsächlich gemessene experimentelle Daten können jedoch oft nicht in Einklang mit idealisierten Annahmen gebracht werden. rnDie vorliegende Arbeit diskutiert die Ergebnisse, welche aus Messungen von Materialien mit niedrigem Restwiderstand erhalten wurden. rnrnAls prototypische Materialien wurden hier hyphenation Heusler-Verbindungen untersucht. Als Material mit einer komplexen Topologie der Fermi-Fläche zeichnet sich dort der Einfluss von Defekten und der Unordnung der Kristallstruktur deutlich ab.rnrnDurch Verwendung von Filmen mit unterschiedlichem Grad der Unordnung können verschiedene Streumechanismen unterschieden werden. Für Co$_{2}$FeSi$_{0.6}$Al$_{0.4}$ and Co$_{2}$FeGa$_{0.5}$Ge$_{0.5}$ zeigt sich ein positiver AHE bei einer Unordnung vom Typ B2 und bei einer induzierten temperaturabh"angigen Streuung, wo hingegen eine Typ DO$_{3}$-Unordnung zusammen mit anderen möglichen intrinsischen Beiträgen einen negativen Effekt hervorruft.rnrnDarüber hinaus wurden die magneto-optische Kerr-Effekte (MOKE) dieser Verbindungen untersucht. Hierfür wurden Beiträge erster Ordnung als Funktion der intrinsischen und extrinsischen Parameter qualitativ analysiert. Auf den Einfluss der kristallinen Ordnung auf Beiträge zweiter Ordnung des MOKE-Signals wird ebenfalls eingegangen.rnrnDes Weiteren wurden dünne Schichten der Heusler-Verbindung Co$_{2}$MnAl auf MgO- und Si-Subs-traten (beide (100)) mit Hochfrequenz-Mag-netron-Sputtern erzeugt. Die zusammensetzung sowie die magnetischen und Transport-Eigenschaften wurden hinsichtlich unterschiedlicher Abscheidebedingungen systematisch untersucht.rnrnInsbesondere zeigt der AHE-Widerstand ein außerordentliches temperaturunabhängiges Verhalten in einem Bereich moderater Magnetfeldstärken von 0 bis 0.6,T. Hierf"ur wurde der nicht-diagonale Transport bei Temperaturen bis zu 300,$^{circ}$C analysiert. Die Daten zeigen die Eignung des Materials für Hall-Sensoren auch oberhalb der Raumtemperatur.rnrnJüngst wurde der Spin Seebeck-Effekt (SSE) entdeckt. Der Effekt aus dem Bereich der Spin-Kaloritronik erzeugt eine Spin-Spannung'' aufgrund eines Temperaturgradienten in magnetischen Materialien. Hier werden vorläufige Messungen des SSE in Ni$_{80}$Fe$_{20}$ und in Heusler-Verbindungen präsentiert.rn

An Investigation of Age-Hardening in a Commercial Copper-Beryllium Alloy

This investigation is concerned with the age-hardening process as exemplified by the aging of a commercial Cu-Be alloy and, in particular, with this pro­cess as determined by X-ray methods. The amount of infor­mation available on age-hardening of commercial alloys is scanty and what information there is, is inaccurate.

Influence of Equatorial Diatom Processes on Si Deposition and Atmospheric CO(2) Cycles at Glacial/Interglacial Timescales

The causes of the glacial cycle remain unknown, although the primary driver is changes in atmospheric CO(2), likely controlled by the biological pump and biogeochemical cycles. The two most important regions of the ocean for exchange of CO(2) with the atmosphere are the equatorial Pacific and the Southern Ocean ( SO), the former a net source and the latter a net sink under present conditions. The equatorial Pacific has been shown to be a Si(OH)(4)-limited ecosystem, a consequence of the low source Si(OH)(4) concentrations in upwelled water that has its origin in the SO. This teleconnection for nutrients between the two regions suggests an oscillatory relationship that may influence or control glacial cycles. Opal mass accumulation rate (MAR) data and delta(15)N measurements in equatorial cores are interpreted with predictions from a one- dimensional Si(OH)(4)-limited ecosystem model (CoSINE) for the equatorial Pacific. The results suggest that equatorial Pacific surface CO(2) processes are in opposite phase to that of the global atmosphere, providing a negative feedback to the glacial cycle. This negative feedback is implemented through the effect of the SO on the equatorial Si(OH)(4) supply. An alternative hypothesis, that the whole ocean becomes Si(OH)(4) poor during cooling periods, is suggested by low opal MAR in cores from both equatorial and Antarctic regions, perhaps as a result of low river input. terminations in this scenario would result from blooms of coccolithophorids triggered by low Si(OH)(4) concentrations.

Size-Fractionated Nitrogen Uptake Measurements in the Equatorial Pacific and Confirmation of the Low Si-High-Nitrate Low-Chlorophyll Condition

The equatorial Pacific Ocean is the largest natural source of CO(2) to the atmosphere, and it significantly impacts the global carbon cycle. Much of the large flux of upwelled CO(2) to the atmosphere is due to incomplete use of the available nitrate (NO(3)) and low net productivity. This high-nutrient low-chlorophyll (HNLC) condition of the equatorial upwelling zone (EUZ) has been interpreted from modeling efforts to be due to low levels of silicate ( Si( OH) 4) that limit the new production of diatoms. These ideas were incorporated into an ecosystem model, CoSINE. This model predicted production by the larger phytoplankton and the picoplankton and effects on air-sea CO(2) fluxes in the Pacific Ocean. However, there were no size-fractionated rates available for verification. Here we report the first size-fractionated new and regenerated production rates (obtained with (15)N - NO(3) and (15)N - NH(4) incubations) for the EUZ with the objective of validating the conceptual basis and functioning of the CoSINE model. Specifically, the larger phytoplankton ( with cell diameters > 5 mu m) had greater rates of new production and higher f-ratios (i.e., the proportion of NO(3) to the sum of NO(3) and NH(4) uptake) than the picoplankton that had high rates of NH(4) uptake and low f-ratios. The way that the larger primary producers are regulated in the EUZ is discussed using a continuous chemostat approach. This combines control of Si(OH)(4) production by supply rate (bottom-up) and control of growth rate ( or dilution) by grazing ( top-down control).

Oceanography during TYDEMAN cruise DCM (DeepChlorMax) to the Equatorial Atlantic

The cruise with RV Tydeman was devoted to study permanently stratified plankton systems in the (sub)tropical ocean, which are characterised by a deep chlorophyll peak between 80 and 150 m. To minimise lateral effects by horizontal transport of nutrients and organic matter from river outflow and upwelling regions, stations were selected in the middle of the North Atlantic Ocean between the continents of America and Africa. (5 - 35° N and 50 - 15° W). Here the vertical distributions of light and nutrients control the abundance and growth of autotrophic algae in the thermically stratified water column. This phytoplankton is numerically dominated by the prokaryotic picoplankters Synechococcus spp. and Prochlorococcus spp., which are smaller than 2 ?m. The productivity of the 100 to 150 m deep euphotic zone can be high, because a high heterotrophic/autotrophic biomass ratio induces a rapid regeneration of nutrients and inorganic carbon. Primary grazers are mainly micro-organisms such as heterotrophic nannoflagellates and ciliates, which feed on the small algae and on bacteria. Heterotrophic bacteria can outnumber the autotrophic algae, because their number is related to the substrate pools of dissolved and particulate dead organic matter. These DOC and detritus pools reach equilibrium at a concentration, where the rate of their production (proportional to algal biomass) equals their mineralisation and sinking rate (proportional to the concentration and weight of POC and detritus). At a relatively low value of the weight-specific loss rates, the equilibrium concentration of these carbon pools and their load of bacteria can be high. The bacterial productivity is proportional to the mineralisation rate, which in a steady state can never be higher than the rate of primary production. Hence the ratio in turnover rate of bacteria and autotrophs tends to be reciprocally proportional to their biomass ratio.

Long chain 1,13- and 1,15-diols in surface sediments ans SST reconstruction for sediment core GeoB6518-1

Although commonly reported in marine and freshwater environments, little is known about the biological sources of long chain alkyl 1,13- and 1,15-diols, and factors controlling their distributions. Here we analyzed the occurrence and distribution of these lipids in a comprehensive set of marine surface sediments and compare their distributions with environmental conditions like sea surface temperature (SST), salinity and nutrient concentrations. Fractional abundances of the C28 1,13-, C30 1,13- and C30 1,15-diols show a strong correlation with SST and based on these results, we propose the Long chain Diol Index (LDI), which expresses the C30 1,15-diol abundance relative to those of C28 1,13-, C30 1,13- and C30 1,15-diols. The LDI shows a strong linear correlation with SST (LDI = 0.033 × SST + 0.095; R2 = 0.969, n = 162) over a temperature range of -3 to 27 °C. Long chain diol distributions in sediments from the South Atlantic close to the Congo River outflow (West Africa) provided a 43 kyr LDI SST record. This record reflects several known climatic events and shows similarities with an alkenone-derived SST record obtained using the same suite of sediments, both in trend and in terms of absolute SST. This confirms the potential of the LDI as a proxy for palaeo-SST reconstruction.

(Table 1) Sediment descriptions and age at DSDP Legs 5 and 63 Holes

Sediments from immediately above basalt basement and from between sections of basalt recovered from Deep Sea Drilling Project Legs 5 and 63 were analyzed by atomic absorption spectroscopy for Mg, Al, Si, Ca, Mn, Fe, Co, Ni, Cu, Zn, and Ba. All of these sediments showed enrichment in Fe and Mn over values typical of detritus supplied to the northeastern Pacific Ocean. X-ray diffractometry and differential chemical leaching indicate that up to 50% of the sediment, by weight, is in amorphous phases and that these phases are rich in Mn, Co, Cu, Ni, and Zn. Multivariate statistical analysis and normative partitioning of the chemical data indicate that much of the excess Fe and other transition elements in the sediment originate from hydrothermal sources.

Grain-size analysis and geochemistry of sediment core GeoB13602-1

Grain-size, terrigenous element and rock magnetic remanence data of Quaternary marine sediments retrieved at the NW African continental margin off Gambia (gravity core GeoB 13602-1, 13°32.71' N, 17°50.96'W) were jointly analyzed by end-member (EM) unmixing methods to distinguish and budget past terrigenous fluxes. We compare and cross-validate the identified single-parameter EM systems and develop a numerical strategy to calculate associated multi-parameter EM properties. One aeolian and two fluvial EMs were found. The aeolian EM is much coarser than the fluvial EMs and is associated with a lower goethite/hematite ratio, a higher relative concentration of magnetite and lower Al/Si and Fe/K ratios. Accumulation rates and grain sizes of the fluvial sediment appear to be primarily constrained by shore distance (i.e., sea-level fluctuations) and to a lesser extent by changes in hinterland precipitation. High dust fluxes occurred during the Last Glacial Maximum (LGM) and during Heinrich Stadials (HS) while the fluvial input remained unchanged. Our approach reveals that the LGM dust fluxes were ~7 times higher than today's. However, by far the highest dust accumulation occurred during HS 1 (~300 g m**-2 yr** -1), when dust fluxes were ~80 fold higher than today. Such numbers have not yet been reported for NW Africa, and emphasize strikingly different environmental conditions during HSs. They suggest that deflation rate and areal extent of HSs dust sources were much larger due to retreating vegetation covers. Beyond its regional and temporal scope, this study develops new, in principle, generally applicable strategies for multi-method end-member interpretation, validation and flux budgeting calibration.

Evaluation of long chain 1,14-alkyl diols in marine sediments as indicators for upwelling and temperature

Long chain alkyl diols form a group of lipids occurring widely in marine environments. Recent studies have suggested several palaeoclimatological applications for proxies based on their distributions, but also revealed uncertainties about their applicability. Here we evaluate the use of long chain 1,14-alkyl diol indices for reconstruction of temperature and upwelling conditions by comparing index values, obtained from a comprehensive set of marine surface sediments, with environmental factors like sea surface temperature (SST), salinity and nutrient concentrations. Previous cultivation efforts indicated a strong effect of temperature on the degree of saturation and the chain length distribution of long chain 1,14-alkyl diols in Proboscia spp., quantified in the diol saturation index (DSI) and diol chain length index (DCI), respectively. However, values of these indices in surface sediments show no relationship with annual mean SST of the overlying water. It remains unknown what determines the DSI, although our data suggests that it may be affected by diagenesis, while the relationship between temperature and DCI may be different for different Proboscia species. In addition, contributions of algae other than Proboscia diatoms may affect both indices, although our data provide no direct evidence for additional long chain 1,14-alkyl diol sources. Two other indices using the abundance of 1,14-diols vs. 1,13-diols and C30 1,15-diols have previously been applied as indicators for upwelling intensity at different locations. The geographical distribution of their values supports the use of 1,14 diols vs. 1,13 diols [C28 + C30 1,14-diols]/[(C28 + C30 1,13-diols) + (C28 + C30 1,14-diols)] as a general indicator for high nutrient or upwelling conditions.

Site characteristics, and major and trace element composition of sediment cores sampled around the Windmill Islands in 1998

To establish a natural background and its temporal and spatial variability for the area around Casey Station in the Windmill Islands, East Antarctica, the authors studied major and trace element concentrations and the distribution of organic matter in marine and lacustrine sediments. A wide range of natural variability in trace metal concentrations was identified between sites and within a time scale of 9 ka (e.g., Ni 5-37 mg/kg, Cu 20-190 mg/kg, Zn 50-300 mg/kg, Pb 4.5- 34 mg/kg). TOC concentrations are as high as 3 wt.% at the marine sites and 20 wt.% at the lacustrine sites, and indicate highly productive ecosystems. These data provide a background upon which the extent of human impact can be established, and existing data indicate negligible levels of disturbance. Geochemical and lithological data for a lacustrine sediment core from Beall Lake confirm earlier interpretation of recent climatic changes based on diatom distribution, and the onset of deglaciation in the northern part of the Windmill Islands between 8.6 and 8.0 ka BP. The results demonstrate that geochemical and lithological data can not only be used to define natural background values, but also to assess long-term climatic changes of a specific environment. Other sites, however, preserve a completely different sedimentary record. Therefore, inferred climatic record, and differences between sites, can be ascribed to differences in elevation, distance from the shore, water depth, and local catchment features. The extreme level of spatial variability seems to be a feature of Antarctic coastal areas, and demonstrates that results obtained from a specific site cannot be easily generalized to a larger area.

Chemistry of pore water and solids, formation factors and salt-corrected porosities of DSDP Site 68-503

Recent discoveries relating to the circulation of fluids within the oceanic crust include the finding of both important fluxes of elements and isotopes into the oceans by ridge-crest hydrothermal convection and important fluxes of heat out of the oceanic crust by convection at ridge crests and at some distance from ridge crests. In the present chapter, I present isotopic, chemical, and physical data from sediments and pore waters of Deep Sea Drilling Project (DSDP) Holes 503A and 503B. These results are modeled in terms of pore-water diffusion, advection, and production to ascertain the relative contribution of these processes at this location, 7.5 m.y. removed from ridge-crest hydrothermal activity. The observations made here contribute to the understanding of chemical and heat transport in oceanic crust of moderate age.

(Table 2) Chemical composition of skeletons of scleractinian non-zooxanthelate corals

The first data on chemical composition of nonreef-building non-zooxanthellate deep-sea corals presented in this publication allow us to identify following tendencies manifested in the biomineralization process. Comparison of concentration levels of some chemical elements in scleractinian corals and ambient ocean waters suggests that corals do not accumulate K in the process of biomineralization and weakly accumulate Mg, whereas Ca, Sr, Si, Al, Ti, Mn, Zn, Cu, Cd, Pb, and Fe are concentrated in skeletons of corals with enrichment coefficients of 10**3 to 10**7. Correlations between components contained in the skeletons of scleractinian corals suggest that the source of Al, Si, Fe, and Ti in them is the clayey constituent of bottom sediments and zooplankton, while trace elements are likely accumulated via bioassimilation from seawater. Such elements as Mn, Sr, Pb, and Cd can structurally substitute Ca in calcite and aragonite. Variations in concentrations of the elements in coral skeletons depending on their habitat depths are fairly significant. As could be expected Ca and Mg concentrations are prone to decrease with depth (R = -0.55 and -0.51, respectively), which can possibly be caused by partial dissolution of carbonate skeletons with increasing depth, whereas the Sr/Ca ratio does not depend on depth.