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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 27 (2000), S. 703-712 
    ISSN: 1432-2021
    Keywords: Key words Fe-Chloritoid ; OH groups ; Dehydration ; Oxidation ; Spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  Triclinic Fe2+ and Fe3+-chloritoid end members, as well as Fe2+-Fe3+-chloritoid solid solutions were synthesized in order to determine the location of the OH groups in the structure and to investigate the possibility of Fe3+ incorporation on the M1B site and the corresponding oxidation mechanism. The samples were analyzed using transmission electron microscopy, electron energy-loss and 57Fe Mössbauer spectroscopy, polarized single-crystal, KBr powder and in situ high-pressure infrared spectroscopy. The structure of a natural triclinic chloritoid was refined by single-crystal X-ray diffraction in order to locate the proton-accepting oxygens in the triclinic structure. The results of valence bond calculations, polarized single-crystal and in situ high-pressure IR spectroscopy revealed that the orientations of the OH dipoles are the same as those in monoclinic chloritoid. The annealing experiments in air show that the incorporation of Fe3+ on M1B increases with temperature. After 3 h at 530 °C all Fe2+ was oxidized to Fe3+ without decomposition of the structure. This also holds true for a heating duration of 24 h. The incorporation of Fe3+ at M1B sites is coupled with a dehydration process starting at about 350 °C during which the H1A protons leave first.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 21 (1994), S. 434-440 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Synthetic pyrope crystals up to 0.5 mm in diameter, substituted by titanium or by titanium plus iron, were grown under defined conditions of P, T, $$f_{O_2 }$$ in the presence of water using a piston-cylinder device. The crystals were characterized by X-ray and microprobe techniques. Their single-crystal optical absorption spectra were measured by means of a microscope-spectrometer. Two absorption bands at 16100 and 22300 cm{cm-1} in the spectra of pale-blue Fe-free Ti-bearing pyropes, grown under reduced conditions, were identified as originating from spin-allowed transitions, derived from 2 T 2g → 2 E g of octahedral Ti3+ ions. The splitting value of the excited 2E g state, 6200 cm-1, and the crystal field parameter of Ti3+ in pyrope Δ 0 = 19 200 cm-1 are both in agreement with literature data. In spectra of brown Fe, Ti-bearing garnets, a broad band at 23000 cm-1 was interpreted as a Fe2+[8] → Ti4+[6] charge-transfer band. The spectral position and width of this band agree with those observed for a FeTi charge transfer band in natural garnets. Fe, Ti-containing garnets synthesized at relatively high oxygen fugacity (10-11,0 atm), which permits a fraction of Fe3+ to enter the garnet, show an additional Fe2+[8] → Fe3+[6] charge transfer band at 19800 cm-1.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 20 (1994), S. 483-488 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract A series of Ti-substituted pyrope crystals was synthesized in the system MgO-(Na2O)-Al2O3-TiO2-SiO2-H2O at PH20 = Ptot between 25 and 30 kbars and 975 and 1000° C, using graphite heated piston-cylinder devices. The crystals, ranging up to 500 μm in diameter, were studied by X-ray, electron-microprobe and FTIR-microscope spectrometric techniques. The pyrope crystals were colourless when hem/mt or mt/wu buffers were used during the synthesis, and pale blue with the wu/iron buffer and in unbuffered runs. Sodium was not found in the synthetic crystals, titanium was always near 0.06 Ti atoms pfu, independent on the Ti-excess used in the starting material. A substitution Al2+[6]+Si4+[4]+4O2-= Ti4+[6]+□[4]+[(OH)3O^5-, providing charge balance for octahedral Ti4+-substitution is found to be compatible with all properties (number, widths, position, integrated intensity) of the stretching vibrations of defect hydroxyls, which have energies 3684, 3568, 3525 cm-1.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 23 (1996), S. 239-240 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 26 (1999), S. 312-321 
    ISSN: 1432-2021
    Keywords: Key-words Synthetic staurolite ; 57Fe-Mössbauer spectroscopy ; Staurolite stoichiometry ; High-pressure staurolite ; Site fractionation of Fe
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  57Fe-Mössbauer spectra of eleven Fe-Mg-bearing staurolite samples, synthesized at 5, 20 and 25 kbar and 680°C, ranging in composition from xFe =1.00 to xFe =0.15, and of two Zn-Fe-bearing staurolite samples, synthesized at 20 kbar and 700°C with xFe =0.10 and xFe =0.32 were collected at room temperature. The spectra reveal that about 80% of Fetot (in case of Fe-Mg-bearing staurolite) and about 70% of Fetot (in case of Fe-Zn-bearing staurolite) are located as Fe2+ at the three subsites Fe1, Fe2 and Fe3 of the tetrahedral T2-site. The refinement of the spectra results in almost identical values for the isomer shift (IS) (±1.0 mm/s) but significantly different values for the quadropole splitting (QS) for the three subsites which is in accordance with the different distortions of these sites. About 8% of Fetot (in case of Fe-Mg-bearing staurolite) and 13% of Fetot (in case of Fe-Zn-bearing staurolite) are located as Fe2+ at the octahedral M4 site, while the remainder percents of Fetot indistinguishably occur as Fe2+ at the octahedral M1 and M2 sites of the kyanite-like part of the structure. Within the whole Fe-Mg-staurolite solid solution series the Mössbauer parameters QS of the sites M4 and (M1, M2) vary systematically with composition whereas IS remains constant. There is a high negative correlation of the total Mg-content with Fe-occupation of all the Fe-bearing sites indicating a continuous substitution of Fe2+ by Mg on all these sites. Synthetic Fe-staurolites show no increasing occupation of the octahedral sites by two-valent cations with pressure, as was assumed by several authors.
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  • 6
  • 7
    Publication Date: 2017-01-23
    Print ISSN: 0003-6951
    Electronic ISSN: 1077-3118
    Topics: Physics
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  • 8
    Publication Date: 2012-09-01
    Print ISSN: 0935-1221
    Electronic ISSN: 1617-4011
    Topics: Geosciences
    Published by Schweizerbart
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  • 9
    Publication Date: 2012-09-01
    Description: Mid- and Far-infrared spectra of a natural ilvaite sample were collected in situ in a diamond-anvil cell (DAC) as a function of pressure. The composition of the natural material is Ca 2+ 0.94 (Fe 2+ 0.61 Mn 2+ 0.40 )(Fe 3+ 1.01 Fe 2+ 0.96 Al 3+ 0.02 Mg 2+ 0.01 )[Si 2.03 O 7 /O/ (OH)] as determined by electron microprobe. One series of DAC experiments was performed at GFZ in the Mid-IR using argon as pressure medium and a Globar as light source. Four pressure series were performed at Bessy II in the Far-IR region using petroleum jelly as pressure medium and synchrotron light. For the Far-IR region we used a custom-made vacuum microscope adapted to an FTIR spectrometer. Pressure-induced changes in the Mid- and Far-IR spectra were analysed via the autocorrelation method for all five pressure series. All five series confirm the monoclinic to orthorhombic phase transition at about 2.3 GPa already known from X-ray diffraction studies. Our results show that incorporation of Mn 2+ does not lower the transition pressure as reported previously. However, the magnitude of the initial monoclinic β angle and the concentration of impurities seem to control the transition pressure. The first evidence of a second pressure-induced phase transition at much higher pressure (between 10 and 11 GPa) is reported here. Both transitions are clearly visible throughout the whole spectral ranges: in the OH-stretching region, the Mid-IR region from 1400 to 400 cm –1 and in the Far-IR region down to 50 cm –1 . The structural change at 10.5 GPa observed via infrared spectroscopy may reflect a pressure-induced suppression of the Jahn–Teller effect of the strongly distorted M2 octahedron. Above 11 GPa and up to 20 GPa no further discontinuities could be detected. One series going in pressure up to 31 GPa may indicate an additional structural change above 20 GPa.
    Print ISSN: 0935-1221
    Electronic ISSN: 1617-4011
    Topics: Geosciences
    Published by Schweizerbart
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  • 10
    Publication Date: 2011-10-13
    Description: The crystal structure of Fe2SiO4 spinel at room temperature was investigated at seven different pressures by X-ray diffraction, using a diamond anvil cell to examine the influence of Fe substitution on ringwoodite behaviour at high pressure. The results compared with those of a pure Mg endmember show that the substitution of Fe into the spinel structure causes only small changes in the compression rate of coordination polyhedra and the distortion of the octahedron. The data show that the compression rate for the octahedron and tetrahedron in (Mg,Fe)2SiO4 can be considered statistically equal for FeO6 and MgO6, as well as for SiO4 in both the endmembers. This shows why almost identical bulk moduli are reported along the solid solution in recent literature.
    Print ISSN: 0026-461X
    Electronic ISSN: 1471-8022
    Topics: Geosciences
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