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  • 1
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 69 (1998), S. 2421-2426 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: Thermomechanical modeling of a sample assembly (sample plus pressure transmitting medium) in a laser-heated diamond–anvil cell (LHDAC) is presented. Finite elements numerical calculation afforded to obtain the temperature distribution and the induced thermal pressure field, showing that a non-negligible pressure increase (called thermal pressure) occurs in the laser-heated zone. When argon is used as a pressure transmitting medium, thermal pressure can reach 20%–30% of the normal pressure measured in the cold zone. This modeling is supported by experimental studies. It is shown that discrepancies between diamond–anvil cell and large volume press experiments on the coesite to stishovite transition are quantitatively explained by the thermal pressure effect. Moreover, thermal pressure also explains the anomalous low thermal expansion coefficient obtained by x-ray diffraction studies in LHDAC. © 1998 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: A simple, rapid, and inexpensive heating-wire technique is used for physical observations at high temperatures. The upper limit is 2000 K in air with platinum-iridium or platinum-rhodium wires and 2700 K with iridium; temperatures up to 3600 K can be achieved under an inert atmosphere with tungsten wires. Raman spectroscopy measurements made up to 1900 K by this technique suggest that the high-temperature harmonic vibrational behavior of corundum (α-Al2O3) results from the cancellation of anharmonic effects. Powder x-ray diffraction experiments with synchrotron radiation show that perovskite (CaTiO3) changes from orthorhombic symmetry to cubic between 1330 and 1530 K, with an intermediate tetragonal phase likely, consistent with λ-type transitions recorded by recent calorimetric measurements. Finally, observations of CaAl2Si2O8 polymorphism has shown the existence of a new metastable phase.
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  • 3
    Electronic Resource
    Electronic Resource
    [s.l.] : Macmillan Magazines Ltd.
    Nature 393 (1998), S. 352-355 
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] The solubility of rare gases in silicate melts and minerals at high pressure is of importance for understanding the early history of the Earth and its present day degassing. Helium, neon, argon, krypton and xenon were originally incorporated into the Earth during its accretion, and have also ...
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  • 4
    ISSN: 1574-6968
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Biology
    Notes: 2C is a lytic phage of Bacillus subtilis, having hydroxymethyluracil (hmUra) replacing thymine (T) in its genome. Little is known of the metabolic advantages of this substitution, in particular for the cascade of regulatory factors ensuring efficient transcription of early, middle and late promoters. Here we report on the isolation of thermosensitive 2C mutants, which could be subdivided in three classes: (1) mutants having 75% replacement of hmUra by thymine in the restrictive conditions; (2) mutants unable to inhibit B. subtilis DNA synthesis in the course of infection; (3) mutants with reduced viral DNA biosynthesis. Different techniques led to these conclusions: differential binding of chromofluorophores with hmUra- and T-containing DNA, quantification of viral DNA by hybridization and buoyant density analysis of labeled DNA in CsCl gradients.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 18 (1992), S. 469-479 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Drop-calorimetry determinations of the isobaric heat capacity (CP) of Mg2GeO4, Ca2GeO4 and CaMgGeO4 have been made up to 1700 K. The thermal expansion coefficient (α) of these olivine germanates has been determined from high-temperature X-ray measurements up to 1500 K. From these measurements and available compressibility data, one calculates that the isochoric heat capacity (CV) exceeds the harmonic limit of Dulong and Petit above 1000–1200 K. Such an intrinsic anharmonic behaviour can be accounted for by introducing anharmonic parameters ai=(∂ ln v i/∂T)V in vibrational modelling of CV. These parameters are calculated from pressure and temperature shifts of the vibrational frequencies as measured by Raman spectroscopy up to 10 GPa at room temperature and up to 1300 K at 1 bar. A comparison of the Raman spectra of the three germanates with those of natural olivines justifies once again the use of germanates as silicate analogues. Extensive Ca,Mg disordering likely takes place in CaMgGeO4, beginning at about 1100 K and leading to unusually high increases of the heat capacity and thermal expansion coefficient.
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  • 6
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract The room-temperature Raman spectra of aragonite, magnesite and dolomite have been recorded up to 30 GPa and 25 GPa, respectively and no phase changes were observed during compression, unlike calcite. The effect of temperature on the room-pressure Raman spectra of calcite, aragonite, magnesite and dolomite is reported up to 800–1100 K. The measured relative pressure and temperature-shifts of the Raman lines are greater for the lattice modes than for the internal modes of the CO3 groups. These shifts are used to calculate the mode anharmonic parameters of the observed Raman modes; they are negative and their absolute values are smaller (close to 0) for the internal CO3 modes than for the lattice modes (4–17 10−5 K−1). The temperature shifts of the lattice modes in calcite are considerably larger than those for dolomite and magnesite, and a marked non-linear increase in linewidth is observed above 400° C for calcite. This is consistent with an increasing relaxational component to the libration of the CO3 groups about their threefold axes, premonitory to the rotational order-disorder transition at higher temperature. This behaviour is not observed for the other calcite structured minerals in this study. We examine systematic variations in the lattice mode frequencies and linewidths with composition, to begin to understand these differences in their anharmonic behaviour. Finally, we have used a simple Debye-Waller model to calculate atomic displacements in calcite, magnesite and dolomite with increasing temperature from the vibrational frequency data, to provide a direct comparison with atomic positional data from high-temperature structure refinements.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 22 (1995), S. 74-86 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract We have measured in-situ Raman spectra of aluminosilicate glasses and liquids with albite (NaAlSi3 O8) and anorthite (CaAl2Si2O8) compositions at high temperatures, through their glass transition range up to 1700 and 2000 K, respectively. For these experiments, we have used a wire-loop heating device coupled with micro-Raman spectroscopy, in order to achieve effective spatial filtering of the extraneous thermal radiation. A major concern in this work is the development of methodology for reliably extracting the first and second order contributions to the Raman scattering spectra of aluminosilicate glasses and liquids from the high temperature experimental data, and analyzing these in terms of vibrational (anharmonic) and configurational changes. The changes in the first order Raman spectra with temperature are subtle. The principal low frequency band remains nearly constant with increasing temperature, indicating little change in the T-O-T angle, and that the angle bending vibration is quite harmonic. This is in contrast to vitreous SiO2, studied previously. Above Tg, intensity changes in the 560–590 cm−1 regions of both sets of spectra indicate configurational changes in the supercooled liquids, associated with formation of additional Al-O-Al linkages, or 3-membered (Al, Si)-containing rings. Additional intensity at 800 cm−1 reflects also some rearrangement of the Si-O-Al network.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Contributions to mineralogy and petrology 107 (1991), S. 484-486 
    ISSN: 1432-0967
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract The heat capacity of glaucophane from the Sesia-Lanza region of Italy having the approximate composition (Na1.93Ca0.05Fe0.02) (Mg2.60Fe0.41) (Al1.83Fe0.15Cr0.01) (Si7.92Al0.08)O22(OH)2 was measured by adiabatic calorimetry between 4.6 and 359.4 K. After correcting the C p 0 data to values for ideal glaucophane, Na2Mg3Al2Si8O22(OH)2 the third-law entropy S 298 0 -S 0 0 was calculated to be 541.2±3.0 J·mol-1·K-1. Our value for S 298 0 -S 0 0 is 12.0 J·mol-1·K-1 (2.2%) smaller than the value of Likhoydov et al. (1982), 553.2±3.0, is within 6.2 J·mol-1·K-1 of the value estimated by Holland (1988), and agrees remarkably well with the value calculated by Gillet et al. (1989) from spectroscopic data, 539 J·mol-1·K-1.
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  • 9
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract The effect of pressure (up to 21 GPa at room temperature) and temperature (up to 1570 K at room pressure) on the Raman spectrum of CaTiO3 is presented. No significant changes, which could be attributed to a major structural change, are observed in the spectra up to 22 GPa. The pressure shifts of the Raman modes can be related to a significant compression of the Ti-O bond. Discontinuous changes in the spectra upon heating may be related to phase changes observed by calorimetry and X-ray diffraction. The important temperature shifts of some low-frequency modes can be related to an increase in the Ti-O-Ti angle in agreement with the X-ray data showing a decrease of the structural distortion with increasing temperature. These data are compared to those available for MgSiO3-perovskite and show that CaTiO3 is a good structural analogue for MgSiO3-perovskite. The present spectroscopic data are used to calculate the specific heat and entropy of CaTiO3. The role of the low frequency modes in the calculations is emphasized. Good agreement is observed between calculated and experimentally determined values in the 0–1300 K temperature range. A similarly defined model is proposed for MgSiO3-perovskite. It is found that the entropy lies between 57 and 64 J/mol/K at 298 K and between 190 and 200 J/mol/K at 1000 K in agreement with the values inferred from experimental equilibrium data. Finally we briefly discuss the values of the Grüneisen parameters of both perovskites inferred from macroscopic and microscopic data.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 20 (1994), S. 556-562 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Raman spectra of Mg2GeO4-olivine were obtained from ambient pressure up to 34 GPa at ambient temperature. Under quasi-hydrostatic pressure conditions, the following modifications in the Raman spectra occur as pressure increases: 1) near 11 GPa, two sharp extra bands appear in the 600–700 cm−1 frequency range, and increase in intensity with respect to the olivine bands; 2) above 22 GPa, these two bands become very intense, and the number, position and relative intensity of the other vibrational bands drastically change; 3) the intensity of sharp bands progressively decreases above 25 GPa. The transformation occurs at lower pressures under non-hydrostatic conditions. During decompression to atmospheric pressure, the high-pressure phase partially reverts to olivine. These observations can be interpreted as the progressive metastable transformation from the olivine structure to a crystalline phase with four-fold coordinated Ge, in which the GeO4 tetrahedra are polymerized. We propose that the metastable high-pressure phase is a structurally disordered spinelloid close to the hypothethical ω- or ɛ*-phase, and forms by a shear mechanism assisted by the development of a dynamical instability in the olivine structure. Implications for the transformations undergone by olivines under far-from-equilibrium conditions (e.g. in subducting lithospheric slabs and in shocks) are discussed.
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