Structural and electrochemical behaviour of sputtered vanadium oxide films: oxygen non-stoichiometry and lithium ion sequestration

Structural and electrochemical aspects of vanadium oxide films recently reported from ICMCB/ENSCPB have been examined using appropriate structural models. It is shown that amorphous films are nonstoichiometric as a result of pre-deposition decomposition of V2O5. It is proposed that the structure of amorphous films corresponds to a nanotextured mosaic of V2O5 and V2O4 regions. Lithium intercalation into these regions is considered to occur sequentially and determined by differences in group electronegativities. Open circuit voltages (OCV) have been calculated for various stoichiometric levels of lithiation using available thermodynamic data with approximate corrections. Sequestration of lithium observed in experiments is shown to be an interfacial phenomenon. X-ray photoelectron spectroscopic observation of the formation of V3+ even when V5+ has not been completely reduced to V4+ is shown to be entirely consistent with the proposed structural model and a consequence of initial oxygen nonstoichiometry. Based on the structural data available on V2O5 and its lithiated products, it is argued that the geometry of VOn polyhedron changes from square pyramid to trigonal bipyramid to octahedron with increase of lithiation. A molecular orbital based energy band diagram is presented which suggests that lithiated vanadium oxides, LixV2O5, become metallic for high values of x

Sea ice and biological production variability reconstructed in the Adélie Basin, East Antarctica, during the late Holocene

第3回極域科学シンポジウム　横断セッション「海・陸・氷床から探る後期新生代の南極寒冷圏環境変動」11月26日（月）、27日（火） ２階ラウン

Condensation of a tetrahedra rigid-body libration mode in HoBaCo4O7 : the origin of phase transition at 355 K

Rietveld profiles, Moessbauer spectra and x-ray absorption fine structure (XAFS) were analyzed through the structural phase transition at Ts = 355 K in HoBaCo4O7. Excess of the oxygen content over O7 was avoided via annealing the samples in argon flow at 600 degree C. Space groups (S.G.) Pbn21c and P63mc were used to refine the structure parameters in the low- and high-temperature phases, respectively. Additionally, the Cmc21 symmetry was considered as a concurrent model of structure of the low-temperature phase. In the high-temperature phase, severe anisotropy of thermal motion of the major part of the oxygen atoms was observed. This anisotropic motion turns to be quenched as the sample is cooled below Ts. The variation of quadrupole splitting near Ts is not similar to a steplike anomaly frequently seen at the charge-ordering transition. We observe instead a dip-like anomaly of the average quadrupole splitting near Ts. Narrow distribution of the electric field gradient (EFG) over different cobalt sites is observed and explained on the basis of point-charge model. XAFS spectra show no evidence of significant difference between YBaCo4O7 (T > Ts) and HoBaCo4O7 (T < Ts). The origin of the transition at Ts is ascribed to the condensation of the libration phonon mode associated with the rigid-body rotational movements of the starlike tetrahedral units, the building blocks of kagome network. It is shown that the condensation of the libration mode is not compatible with translation symmetry for the hexagonal S.G., but compatible for the orthorhombic S.G. The orthorhombic lattice parameters and EFG components (Vxx, Vyy, Vzz) vary smoothly with temperature at approaching Ts and closely follow each other.Comment: 13 figure

Geometrical quadrupolar frustration in DyB4_4

Physical properties of DyB$_4$ have been studied by magnetization, specific heat, and ultrasonic measurements. The magnetic entropy change and the ultrasonic properties in the intermediate phase II indicate that the degeneracy of internal degrees of freedom is not fully lifted in spite of the formation of magnetic order. The ultrasonic attenuation and the huge softening of $C_{44}$ in phase II suggests existence of electric-quadrupolar (orbital) fluctuations of the 4$f$-electron. These unusual properties originate from the geometrical quadrupolar frustration.Comment: 4 pages, 4 figures, accepted for publication in Journal of the Physical Society of Japa

Pressure induced Metallization of Fordite SnNb₂O₆ from First Principles

From DFT based calculations establishing energy-volume equations of state, a proposition of high pressure candidate structures with reduced volumes, namely columbite and trirutile are proposed for fordite mineral SnNb₂O₆. The key effect is the destabilization of divalent tin in fordite towards tetravalent state upon compression. This is helped with smaller size tetravalent tin. The remarkable electronic structure change is the transformation from semi-conducting fordite to metallic high pressure forms thanks to the electron transfer from Sn to Nb and O as quantified from charge density analyses.Keywords: High pressure, Fordite, DFT, Density of states, Equation of statesKeywords: High pressure, Fordite, DFT, Density of states, Equation of state

The past : a compass for future earth

Antarctic sea ice impacts on the ocean-atmosphere heat and gas fluxes, the formation of deep and intermediate waters, the nutrient distribution and primary productivity, the so-called &#8216;biological carbon pump&#8217;, one of the most active in the global ocean. In this study, we explore the link between sea ice dynamic, biological production and nutrient cycling during the late Holocene (the last 2,000 yrs) in the Adélie Basin, East Antarctica, from the well-dated sediments of the Ocean Drilling Program (ODP) Site U1357. This archive, composed from ~32 meters of seasonal to annual laminated diatomaceous sequences, allows reconstructions at an unprecedented time resolution (5-10 yrs). Our study combines records of diatom census counts and diatom-specific biomarkers (a ratio (D/T) of di- and tri-unsaturated Highly Branched Isoprenoid lipids (HBI)) as indicators of sea ice and biological production changes, XRF data as markers for terrigenous inputs and bulk nitrogen isotopes (d15N) and d15N on chlorins as proxies for reconstructing nitrogen cycle. The diatom and HBI records reveal five distinct periods. From 0 to 350 yrs AD, decreasing occurrences of sea ice-related diatom species (e.g. Fragilariopsis curta + F. cylindrus) together with low D/T values and increasing open ocean diatom species (large centrics, Chaetoceros Resting Spores (CRS)) document a progressive decline of sea ice presence during the year (>9 months per year) with spring melting occurring earlier in the year and autumn sea ice formation appearing later. In contrast, between 350 and 750 yrs AD, high production of open ocean diatom species and low low D/T values and sea ice related species indicate a short duration of sea ice cover (~10 months per year) is illustrated by a pronounced increase of sea ice-associated diatom species and high D/T values. Between ~1400 and 1850 yrs AD, seasonal sea ice strongly declines (<~7 months per year) as a result of early spring melting (increasing CRS production) and late autumn waxing (high occurrences of Thalassiosira antarctica). Longer growing seasons promoted a substantial development of phytoplankton communities (especially large centric diatoms) that conducted to lower D/T values. Consistent with diatom and HBI reconstructions, XRF data show higher Fe/Al and Zr/Al ratios values during inferred warmer periods and lower ratio values during inferred cooler and icier periods, thus supporting a strong impact of the sea ice seasonal cycle on glacial runoffs. The link between sea ice conditions, biological production and nutrient cycling is still being explored and we will discuss its relationship by combining all the cited records cited above with the d15N records that we are currently generated. Based on our results, we find that sea ice dynamic and associated diatom production in the Adélie Basin revealed an opposite climatic trend than that identified in the Northern Hemisphere for the last 2000 years. The 'Little Ice Age' (1400-1850 yrs AD) or the 'Dark Ages' (400-750 yrs AD) corresponded to warmer climate conditions in the Adélie Basin, while the 'Roman Warm Period' (0-350 yrs AD) or the 'Medieval Warm Period' (900-1200 yrs AD) were associated to colder conditions. We therefore emphasize that Northern and Southern Hemisphere climate evolved in anti-phase seesaw pattern during the late Holocene

Anomalous NMR Spin-Lattice Relaxation in SrB_{6} and Ca_{1-x}La_{x}B_{6}

We report the results of {11}B nuclear magnetic resonance (NMR) measurements of SrB_{6} and Ca_{0.995}La_{0.05}B_{6} below room temperature. Although the electrical resistivities of these two materials differ substantially, their {11}B-NMR responses exhibit some strikingly common features. Both materials exhibit ferromagnetic order, but their {11}B-NMR spectra reveal very small hyperfine fields at the Boron sites. The spin lattice relaxation T_{1}^{-1} varies considerably with external field but changes with temperature only below a few K. We discuss these unusual results by considering various different scenarios for the electronic structure of these materials.Comment: Accepted for publication in Phys. Rev. B Rapid communication, 4 pages, 3 figures. This manuscript replaces an earlier version and includes some minor changes in the text and in Fig.

Holocene climate variations in the western Antarctic Peninsula: evidence for sea ice extent predominantly controlled by changes in insolation and ENSO variability

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Holocene climate variations in the western Antarctic Peninsula: evidence for sea ice extent predominantly controlled by changes in insolation and ENSO variability

The West Antarctic ice sheet is particularly sensitive to global warming and its evolution and impact on global climate over the next few decades remains difficult to predict. In this context, investigating past sea ice conditions around Antarctica is of primary importance. Here, we document changes in sea ice presence, upper water column temperatures (0-200 m) and primary productivity over the last 9000 yr BP (before present) in the western Antarctic Peninsula (WAP) margin from a sedimentary core collected in the Palmer Deep Basin. Employing a multi-proxy approach, based on the combination of two biomarkers proxies (highly branched isoprenoid (HBI) alkenes for sea ice and TEXL 86 for temperature) and micropaleontological data (diatom assemblages), we derived new Holocene records of sea ice conditions and upper water column temperatures. The early Holocene (9000-7000 yr BP) was characterized by a cooling phase with a short sea ice season. During the midHolocene (similar to 7000-3800 yr BP), local climate evolved towards slightly colder conditions and a prominent extension of the sea ice season occurred, promoting a favorable environment for intensive diatom growth. The late Holocene (the last similar to 100 yr) was characterized by warmer temperatures and increased sea ice presence, accompanied by reduced local primary productivity, likely in response to a shorter growing season compared to the early or mid-Holocene. The gradual increase in annual sea ice duration over the last 7000 yr might have been influenced by decreasing mean annual and spring insolation, despite increasing summer insolation. We postulate that, in addition to precessional changes in insolation, seasonal variability, via changes in the strength of the circumpolar Westerlies and upwelling activity, was further amplified by the increasing frequency/amplitude of the El Nino-Southern Oscillation (ENSO). However, between 3800 and 2100 yr BP, the lack of correlation between ENSO and climate variability in the WAP suggests that other climatic factors might have been more important in controlling WAP climate at this time