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  • 2015-2019  (5)
  • 1
    Publication Date: 2019
    Description: 〈span〉〈div〉Abstract〈/div〉Topaz [Al〈sub〉2〈/sub〉SiO〈sub〉4〈/sub〉(F,OH)〈sub〉2〈/sub〉] is a subduction-related mineral that is found in metasediments and has a large pressure and temperature stability field. Here, we use luminescence spectroscopy of Cr〈sup〉3+〈/sup〉 to probe the Al site in topaz at pressures up to ~60 GPa, which corresponds to a depth of ~1400 km in the Earth. This technique allows us to probe all three unique Al environments (i.e., [AlO〈sub〉4〈/sub〉(OH)〈sub〉2〈/sub〉]〈sup〉7–〈/sup〉, [AlO〈sub〉4〈/sub〉(F)〈sub〉2〈/sub〉]〈sup〉7–〈/sup〉, and [AlO〈sub〉4〈/sub〉OH,F]〈sup〉7–〈/sup〉) simultaneously under high pressure. We find that the R-line luminescence from all three Al environments shift linearly to longer wavelength to ~40 GPa. Above ~40 GPa, they shift nonlinearly and begin to flatten out at ~48 GPa, with a pressure shift of ~0 cm〈sup〉–1〈/sup〉/GPa from ~48–55 GPa. Our results, combined with previous high-pressure single-crystal X-ray diffraction studies to ~45 GPa, strongly indicate that there is a change in the compression mechanism in topaz above ~40 GPa. Our high-pressure room-temperature results show that the metastable persistence of topaz on compression represents one of the most extreme cases among tetrahedrally coordinated silicates.〈/span〉
    Print ISSN: 0003-004X
    Electronic ISSN: 1945-3027
    Topics: Geosciences , Physics
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  • 2
    Publication Date: 2016-06-03
    Description: Cr 3+ luminescence of the green Cr-bearing variety of spodumene (LiAlSi 2 O 6 ) has been studied under hydrostatic conditions up to ~15 GPa. R-line luminescence is a particularly sensitive site-specific probe of the Al-site, and high-pressure phase transitions that affect the symmetry or electron density at this site should produce obvious changes in the luminescence spectra. Thus, the nature of Cr 3+ luminescence is probed across known and possible phase transitions in spodumene. Discontinuous shifts of the R-lines and their sidebands to higher energy at 3.2 GPa are associated with the C 2/ c to P 2 1 / c phase transition. Both R-lines and sidebands shift to lower energy after the 3.2 GPa transition up to ~15 GPa. The C 2/ c to P 2 1 / c phase transition is confirmed to be first order in nature based on its observed hysteresis on decompression, and R-line and sideband measurements give no evidence of a second proposed transition up to ~15 GPa. The splitting between the R 1 and R 2 bands is dramatically enhanced by pressure, with the split decreasing at the phase transition. These trends correspond to pressure-induced shifts in the distortion of the M1 site, and a likely shift in off-centeredness of the Cr 3+ ion. Pressure-induced decreases in line widths are consistent with the R-lines shifting at slower rates than the phonons to which they are most closely coupled, as demonstrated by large pressure shifts of vibronic peaks. Observations of a pressure-induced cross-over between the 4 T 2 and 2 E levels of the Cr 3+ ion indicate that spodumene undergoes a shift from an intermediate strength crystal field environment to a high strength crystal field environment at pressures between ambient and 3.2 GPa.
    Print ISSN: 0003-004X
    Electronic ISSN: 1945-3027
    Topics: Geosciences
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  • 3
    Publication Date: 2019
    Description: 〈span〉〈div〉Abstract〈/div〉The elasticity of a sequence of SiO〈sub〉2〈/sub〉-TiO〈sub〉2〈/sub〉 glasses is examined at high pressures and temperatures. A primary goal is to determine how the previously proposed substitution of fivefold-coordinated Ti at low concentrations of Ti and fourfold-coordinated Ti at higher concentrations affects the elastic properties of these glasses. The effect of changing Ti content on the bulk moduli of these glasses is monotonic, and no systematic effect of possible coordination changes is observed. In contrast, there is an apparent decrease in the pressure derivative of the bulk modulus above ~3 wt% TiO〈sub〉2〈/sub〉. This change occurs at a similar composition to that at which a transition from predominantly fivefold to fourfold of Ti has been proposed to occur in these glasses. Hence, this shift in the pressure derivative of the bulk modulus is attributed to a stiffening of the equation of state of these glasses generated by the substitution of fivefold Ti species relative to TiO〈sub〉4〈/sub〉 units. Our results provide rationales for the onset of coordination changes producing a minimal change in the equation of state of silicate melts/glasses, and for bulk moduli determined at ambient pressure producing relatively accurate silicate melt volumes even within liquids that have begun to undergo coordination changes. Thus, our results support the general validity of single equation of state formulations that describe the densities of silicate melts through the transition zone and shallow lower mantle.〈/span〉
    Print ISSN: 0003-004X
    Electronic ISSN: 1945-3027
    Topics: Geosciences , Physics
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  • 4
    Publication Date: 2018-05-30
    Description: The thermal conductivity of iron alloys at high pressures and temperatures is a critical parameter in governing ( a) the present-day heat flow out of Earth's core, ( b) the inferred age of Earth's inner core, and ( c) the thermal evolution of Earth's core and lowermost mantle. It is, however, one of the least well-constrained important geophysical parameters, with current estimates for end-member iron under core-mantle boundary conditions varying by about a factor of 6. Here, the current state of calculations, measurements, and inferences that constrain thermal conductivity at core conditions are reviewed. The applicability of the Wiedemann-Franz law, commonly used to convert electrical resistivity data to thermal conductivity data, is probed: Here, whether the constant of proportionality, the Lorenz number, is constant at extreme conditions is of vital importance. Electron-electron inelastic scattering and increases in Fermi-liquid-like behavior may cause uncertainties in thermal conductivities derived from both first-principles-associated calculations and electrical conductivity measurements. Additional uncertainties include the role of alloying constituents and local magnetic moments of iron in modulating the thermal conductivity. Thus, uncertainties in thermal conductivity remain pervasive, and hence a broad range of core heat flows and inner core ages appear to remain plausible.
    Print ISSN: 0084-6597
    Electronic ISSN: 1545-4495
    Topics: Geosciences , Physics
    Published by Annual Reviews
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  • 5
    Publication Date: 2019-10-28
    Print ISSN: 0094-8276
    Electronic ISSN: 1944-8007
    Topics: Geosciences , Physics
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