Magnesium based nanoparticles for hydrogen storage

Questo lavoro riguarda la sintesi e caratterizzazione di nanoparticelle basate sul magnesio per l'immagazzinamento di idrogeno. Le nanoparticelle sono state cresciute mediante Inert Gas Condensation, una tecnica aerosol in cui il materiale viene sublimato e diretto verso i substrati tramite un flusso di gas inerte, e caratterizzate attraverso microscopia elettronica e diffrazione di raggi X. Queste operazioni sono state eseguite presso il Dipartimento di Fisica e Astronomia dell'Università di Bologna. Sono stati sintetizzati due tipi di particelle: nel primo il magnesio viene deposto direttamente sul substrato, nel secondo esso incontra un flusso di ossigeno prima di depositarsi sulla superficie. In questo modo si formano delle particelle con struttura core-shell in cui la parte interna è formata da magnesio e quella esterna dal suo ossido. La presenza di una shell consistente dovrebbe permettere, secondo il modello di deformazioni elastiche, di diminuire il valore assoluto dell'entropia di formazione dell'idruro di magnesio, condizione necessaria affinché il desorbimento di idrogeno possa avvenire in maniera più agevole rispetto a quanto non accada col materiale bulk. Tutti i campioni sono stati ricoperti di palladio, il quale favorisce la dissociazione della molecola di idrogeno. La capacità di assorbimento dell'idrogeno da parte dei campioni è stata studiata mediante idrogenografia, una tecnica ottica recentemente sviluppata in cui la quantità di gas assorbita dal materiale è legata alla variazione di trasmittanza ottica dello stesso. Le misure sono state eseguite presso l'Università Tecnica di Delft. I risultati ottenuti evidenziano che le nanoparticelle di solo magnesio mostrano dei chiari plateau di pressione corrispondenti all'assorbimento di idrogeno, tramite cui sono stati stimati i valori di entalpia di formazione. Al contrario, i campioni con struttura core-shell, la cui crescita rappresenta di per sé un risultato interessante, non presentano tale comportamento.

Fluorescent-magnetic hybrid nanoparticles induce a dose-dependent increase in proinflammatory response in lung cells in vitro correlated with intracellular localization

Iron-platinum nanoparticles embedded in a poly(methacrylic acid) (PMA) polymer shell and fluorescently labeled with the dye ATTO 590 (FePt-PMA-ATTO-2%) are investigated in terms of their intracellular localization in lung cells and potential to induce a proinflammatory response dependent on concentration and incubation time. A gold core coated with the same polymer shell (Au-PMA-ATTO-2%) is also included. Using laser scanning and electron microscopy techniques, it is shown that the FePt-PMA-ATTO-2% particles penetrate all three types of cell investigated but to a higher extent in macrophages and dendritic cells than epithelial cells. In both cell types of the defense system but not in epithelial cells, a particle-dose-dependent increase of the cytokine tumor necrosis factor alpha (TNFalpha) is found. By comparing the different nanoparticles and the mere polymer shell, it is shown that the cores combined with the shells are responsible for the induction of proinflammatory effects and not the shells alone. It is concluded that the uptake behavior and the proinflammatory response upon particle exposure are dependent on the time, cell type, and cell culture.

Flame Synthesis of Complex Fluoride-Based Nanoparticles as Upconversion Phosphors

Recent improvements in precursor chemistry, reactor geometry and run conditions extend the manufacturing capability of traditional flame aerosol synthesis of oxide nanoparticles to metals, alloys and inorganic complex salts. As an example of a demanding composition, we demonstrate here the one-step flame synthesis of nanoparticles of a 4-element non-oxide phosphor for upconversion applications. The phosphors are characterized in terms of emission capability, phase purity and thermal phase evolution. The preparation of flame-made beta-NaYF4 with dopants of Yb, Tm or Yb, Er furthermore illustrates the now available nanoparticle synthesis tool boxes based on modified flamespray synthesis from our laboratories at ETH Zurich. Since scaling concepts for flame synthesis, including large-scale filtration and powder handling, have become available commercially, the development of industrial applications of complex nanoparticles of metals, alloys or most other thermally stable, inorganic compounds can now be considered a feasible alternative to traditional top-down manufacturing or liquid-intense wet chemistry.

Combined Ultrasmall Superparamagnetic Particles of Iron Oxide–Enhanced and Diffusion-weighted Magnetic Resonance Imaging Facilitates Detection of Metastases in Normal-sized Pelvic Lymph Nodes of Patients with Bladder and Prostate Cancer

Background Conventional cross-sectional imaging with computed tomography and magnetic resonance imaging (MRI) has limited accuracy for lymph node (LN) staging in bladder and prostate cancer patients. Objective To prospectively assess the diagnostic accuracy of combined ultrasmall superparamagnetic particles of iron oxide (USPIO) MRI and diffusion-weighted (DW) MRI in staging of normal-sized pelvic LNs in bladder and/or prostate cancer patients. Design, setting, and participants Examinations with 3-Tesla MRI 24–36 h after administration of USPIO using conventional MRI sequences combined with DW-MRI (USPIO-DW-MRI) were performed in 75 patients with clinically localised bladder and/or prostate cancer staged previously as N0 by conventional cross-sectional imaging. Combined USPIO-DW-MRI findings were analysed by three independent readers and correlated with histopathologic LN findings after extended pelvic LN dissection (PLND) and resection of primary tumours. Outcome measurements and statistical analysis Sensitivity and specificity for LN status of combined USPIO-DW-MRI versus histopathologic findings were evaluated per patient (primary end point) and per pelvic side (secondary end point). Time required for combined USPIO-DW-MRI reading was assessed. Results and limitations At histopathologic analysis, 2993 LNs (median: 39 LNs; range: 17–68 LNs per patient) with 54 LN metastases (1.8%) were found in 20 of 75 (27%) patients. Per-patient sensitivity and specificity for detection of LN metastases by the three readers ranged from 65% to 75% and 93% to 96%, respectively; sensitivity and specificity per pelvic side ranged from 58% to 67% and 94% to 97%, respectively. Median reading time for the combined USPIO-DW-MRI images was 9 min (range: 3–26 min). A potential limitation is the absence of a node-to-node correlation of combined USPIO-DW-MRI and histopathologic analysis. Conclusions Combined USPIO-DW-MRI improves detection of metastases in normal-sized pelvic LNs of bladder and/or prostate cancer patients in a short reading time.

Annotated record and chemical composition of iron-manganese nodules from the Baltic Sea

Iron-manganese concretions, closely related to lacustrine ores and deep sea manganese nodules, are presently forming in different parts of Gulfs of Bothnia and Finland. They can be divided according to physical form into three distinct groups: (1) round pea-shaped concretions, (2) ring-shaped concrections, and (3) flat sheets and crusts of concretionary material. A definite correlation was found to exist between the form i.e. type of concretions and their chemical composition (Mn/Fe ratio). Trace element concentrations were generally rather high, although not as high as in deep sea manganese nodules. X-ray and DTA was used to study the mineralogy and crystal structure of the concretions. Surface concentrations and geographical distribution of the concretions were estimated on the basis of samples, diving observations and echo-grams.

Geochemistry and oxygen and iron isotope ratios of mafic rocks

Recycling of oceanic crust into the deep mantle via subduction is a widely accepted mechanism for creating compositional heterogeneity in the upper mantle and for explaining the distinct geochemistry of mantle plumes. The oxygen isotope ratios (d18O) of some ocean island basalts (OIB) span values both above and below that of unmetasomatised upper mantle (5.5 ± 0.4 per mil) and provide support for this hypothesis, as it is widely assumed that most variations in d18O are produced by near-surface low-temperature processes. Here we show a significant linear relationship between d18O and stable iron isotope ratios (d57Fe) in a suite of pristine eclogite xenoliths. The d18O values of both bulk samples and garnets range from values within error of normal mantle to significantly lighter values. The observed range and correlation between d18O and d57Fe is unlikely to be inherited from oceanic crust, as d57Fe values determined for samples of hydrothermally altered oceanic crust do not differ significantly from the mantle value and show no correlation with d18O. It is proposed that the correlated d57Fe and d18O variations in this particular eclogite suite are predominantly related to isotopic fractionation by disequilibrium partial melting although modification by melt percolation processes cannot be ruled out. Fractionation of Fe and O isotopes by removal of partial melt enriched in isotopically heavy Fe and O is supported by negative correlations between bulk sample d57Fe and Cr content and bulk sample and garnet d18O and Sc contents, as Cr and Sc are elements that become enriched in garnet- and pyroxene-bearing melt residues. Melt extraction could take place either during subduction, where the eclogites represent the residues of melted oceanic lithosphere, or could take place during long-term residence within the lithospheric mantle, in which case the protoliths of the eclogites could be of either crustal or mantle origin. This modification of both d57Fe and d18O by melting processes and specifically the production of low-d18O signatures in mafic rocks implies that some of the isotopically light d18O values observed in OIB and eclogite xenoliths may not necessarily reflect near-surface processes or components.

In-situ Iron isotope measurements and mineral compositions from ODP Hole 206-1256D and IODP Hole 335-U1256D

In-situ Fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the Fe isotopic composition of Fe-Ti-oxides and Fe-sulfides of the different lithologies of the drilled rocks from IODP Hole 1256D (eastern equatorial Pacific; 15 Ma crust formed at the East Pacific Rise). Most igneous rocks normally have a very restricted range in their 56Fe/54Fe ratio. In contrast, Fe isotope compositions of hot fluids (> 300 °C) from mid-ocean-ridge spreading centers define a narrow range that is shifted to lower delta 56Fe values by 0.2 per mil - 0.5 per mil as compared to igneous rocks. Therefore, it is expected that mineral phases that contain large amounts of Fe are especially affected by the interaction with a fluid that fractionates Fe isotopes during exsolution/precipitation of those minerals. We have used a femtosecond UV-Laser ablation system to determine mineral 56Fe/54Fe ratios of selected samples with a precision of < 0.1 per mil (2 sigma level) at micrometer-scale. We have found significant variations of the delta 56Fe (IRMM-014) values in the minerals between different samples as well as within samples and mineral grains. The overall observed scale of delta 56Fe (magnetite) in 1256D rocks ranges from - 0.12 to + 0.64 per mil, and of delta 56Fe (ilmenite) from - 0.77 to + 0.01 per mil. Pyrite in the lowermost sheeted dike section is clearly distinguishable from the other investigated lithological units, having positive delta 56Fe values between + 0.29 and + 0.56 per mil, whereas pyrite in the other samples has generally negative delta 56Fe values from - 1.10 to - 0.59 permil. One key observation is that the temperature dependent inter-mineral fractionations of Fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values, while synthesized, well equilibrated magnetite-ilmenite pairs are compatible with the theoretical predictions. Theoretical considerations including beta-factors of different aqueous Fe-chlorides and Rayleigh-type fractionations in the presence of a hydrous, chlorine-bearing fluid can explain this observation. The disagreement between observed and theoretical equilibrium fractionation, the fact that magnetite, in contrast to ilmenite shows a slight downhole trend in the delta 56Fe values, and the observation of small scale heterogeneities within single mineral grains imply that a general re-equilibration of the magnetite-ilmenite pairs is overprinted by kinetic fractionation effects, caused by the interaction of magnetite/ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling, or incomplete re-equilibration at low temperatures. Furthermore, the observation of significant small-scale variations in the 56Fe/54Fe ratios of single minerals in this study highlights the importance of high spatial-resolution-analyses of stable isotope ratios for further investigations.

Chemical composition of iron-manganese and phosphate rocks from aseismic ridges of the Indian Ocean and from the continental slope of the Southeast Africa

Study of chemical composition of 26 samples collected at depths from 400 to 1400 m on vertex surfaces of the Southeast Indian Ridge, Mascarene Ridge, Madagascar Ridge, and Mozambique Ridge, as well as on the upper part of the Southeast Africa continental slope showed that the samples represent three groups of rocks: 1) low phosphate or phosphate-free ferromanganese rocks, 2) phosphate ferromanganese rocks 3) phosphorites and phosphatized limestones.

Mineralogy and major element oxide composition of sediments from ODP Hole 172-1063D

Dansgaard-Oeschger (D-O) cycles in sediment at Site 1063 are characterized by distinct fluctuations in physical properties. Stadials are marked by low bulk density and interstadials by high bulk density. Compressional (P-)wave velocity is in phase with bulk density over some but not all depth intervals. Four of the D-O cycles straddling the oxygen isotope Stage 4/5 boundary have been studied in detail to understand the origin of the physical properties changes. Sediment on the Bermuda Rise is comprised of three main components: calcite, aluminosilicate minerals, and biogenic silica. Calcite concentrations vary from 1% to 43% of bulk sediment and are highest during interstadials. Aluminosilicate concentrations vary from 52% to 92% of bulk sediment and are highest during stadials. The major element ratios Al2O3/TiO2 and K2O/Al2O3 show increases across bulk density cycles, suggesting a change in the composition of aluminosilicates. This interpretation is supported by mineralogical analyses, which show a subtle change in clay composition. Biogenic silica concentrations vary from 0% to 23% of bulk sediment and are also highest during stadials. However, the abundance of silica varies significantly from one D-O cycle to another. Silt and fine sand abundance also increase during the first of the four stadials. This coarsening of sediment coincides with the increase in biogenic silica. The low grain density and high porosity associated with biogenic silica result in intervals of low bulk-sediment density. The abundance of biogenic silica closely matches P-wave velocity, suggesting that silica imparts a greater rigidity to the sediment.