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  • 1
    Monograph available for loan
    Monograph available for loan
    Amsterdam : Elsevier Science
    Call number: 17/M 20.93246
    Type of Medium: Monograph available for loan
    Pages: vii, 708 Seiten , Graphiken
    Edition: 2nd ed
    ISBN: 978-0-444-63709-6
    Classification: C.4.
    Language: English
    Note: 1.1. The Early History of Glass; 1.2. Glass and Science; 1.3. The Discovery of Natural Melts; 1.4. The Physical Chemistry of Melts; 1.5. Summary Remarks; References; Chapter 2. Glass Versus Melt; 2.1. Relaxation; 2.2. Glass Transition; 2.3. Configurational Properties; 2.4. Summary Remarks; References; Chapter 3. Glasses and Melts vs. Crystals; 3.1. Basics of Silicate Structure 3.2. Thermodynamic Properties3.3. Liquid-Like Character of Crystals; 3.4. Summary Remarks; References; Chapter 4. Melt and Glass Structure -- Basic Concepts; 4.1. Bond Length, Bond Angle, and Bond Strength in Silicates; 4.2. Network-Formers; 4.3. Network-Modifying Cations and Linkage between Structural Units; 4.4. Bonding, Composition and Effects on Melt Properties; 4.5 Mixing, Order, and Disorder; 4.6. Summary Remarks; References; Chapter 5. Silica -- A Deceitful Simplicity; 5.1. An Outstanding Oxide; 5.2. Physical Properties; 5.3. Structure of SiO2 Glass and Melt 5.4. Effects of Pressure and Temperature5.5. Summary Remarks; References; Chapter 6. Binary Metal Oxide-Silica Systems -- I. Physical Properties; 6.1. Phase Relationships; 6.2. Thermodynamics of Mixing; 6.3. Volume and Transport Properties; 6.4. Summary Remarks; References; Chapter 7. Binary Metal Oxide-Silica Systems -- II. Structure; 7.1. Pseudocrystalline Models of Melt Structure; 7.2. Thermodynamic Modeling and Melt Structure; 7.3. Numerical Simulation of Melt Structure; 7.4. Structure from Direct Measurements; 7.5. Structure and Melt Properties; 7.6. Summary Remarks; References Chapter 8. Aluminosilicate Systems -- I. Physical Properties8.1. Phase Relationships; 8.2. Thermodynamics of Mixing; 8.3. Volume and Viscosity; 8.4. Summary Remarks; References; Chapter 9. Aluminosilicate Systems -- II. Structure; 9.1. Binary Al2O3-Bearing Glasses and Melts; 9.2. Meta-Aluminosilicate Glasses and Melts (SiO2-M1/xAlO2); 9.3. Peralkaline Aluminosilicate Glasses and Melts; 9.4. Pressure and the Structure of Aluminosilicate Melts; 9.5. Structure and Properties of Aluminosilicate Melts; 9.6. Summary Remarks; References; Chapter 10. Iron-bearing Melts -- I. Physical Properties 10.1 Ferrous and Ferric Iron10.2. Phase Equilibria; 10.3. Iron Redox Reactions; 10.4. Physical Properties; 10.5. Summary Remarks; References; Chapter 11. Iron-bearing Melts -- II. Structure; 11.1. Ferric Iron; 11.2. Ferrous Iron; 11.3. Ferric and Ferrous Iron in Silicate Melts at High Temperature; 11.4. Iron in Silicate Melts and Glasses at High Pressure; 11.5. Summary Remarks; References; Chapter 12. The Titanium Anomalies; 12.1. Phase Relations and Glass Formation; 12.2. Physical Properties; 12.3. Structure of Titanosilicate Glasses and Melts; 12.4. High-Temperature Studies
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  • 2
    Monograph available for loan
    Monograph available for loan
    Amsterdam [u.a.] : Elsevier
    Associated volumes
    Call number: 10/M 09.0224
    In: Developments in geochemistry
    Description / Table of Contents: Contents: 1. The Discovery of Silicate Melts. An Industrial and Geological Perspective. 2. Glass Versus Melt. 3. Glasses and Melts vs. Crystals. 4. Melt and Glass Structure - Basic Concepts. 5. Silica - A Deceitful Simplicity. 6. Binary Metal Oxide-Silica Systems I. Physical Properties.7. Binary Metal Oxide-Silica Systems II. Structure. 8. Aluminosilicate Systems I. Physical Properties. 9. Aluminosilicate Systems II. Structure. 10. Iron-bearing Melts I. Physical Properties. 11. Iron-bearing Melts II. Structure. 12. The Titanium Anomalies. 13. Phosphorus. 14. Water - An Elusive Component. 15. Volatiles I. The System C-O-H-S. 16. Volatiles II. Noble Gases and Halogens. 17. Natural Melts.
    Type of Medium: Monograph available for loan
    Pages: xv, 544 S.
    ISBN: 0444520112
    Series Statement: Developments in geochemistry 10
    Classification: A.3.8.
    Location: Reading room
    Branch Library: GFZ Library
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  • 3
    Monograph available for loan
    Monograph available for loan
    Amsterdam [u.a.] : Elsevier
    Associated volumes
    Call number: 10/FHD 122
    In: Developments in geochemistry
    Type of Medium: Monograph available for loan
    Pages: VII, 354 S.
    ISBN: 044442959X
    Series Statement: Developments in geochemistry 4
    Language: English
    Location: Reading room
    Branch Library: GFZ Library
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  • 4
    Publication Date: 1996-04-01
    Description: The isostructural lithium (Li2SiO3) and sodium (Na2SiO3) metasilicates have been investigated from room temperature up to the melting point by single-crystal Raman spectroscopy and energy-dispersive X-ray powder diffraction. The unit-cell parameters and Raman frequencies of Li2SiO3 vary regularly with temperature up to the melting point, which is consistent with the lack of premelting effects in calorimetric measurements. In contrast, Na2SiO3 undergoes a transition at about 850 K from orthorhombic Cmc 21 symmetry, to a lower symmetry (possibly Pmc 21), and shows near 1200 K changes in the Raman spectra that correlate well with the premelting effects as determined from calorimetry observations. In both compounds, a high alkali mobility likely sets in several hundreds of degrees below the melting point. Premelting in Na2SiO3 is associated with extensive deformation of the silicate chains as evidenced near the melting point by similarities in the Raman spectra of the crystalline and liquid phases. ©1996 Springer-Verlag
    Print ISSN: 0342-1791
    Electronic ISSN: 1432-2021
    Topics: Chemistry and Pharmacology , Geosciences , Physics
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  • 5
    Publication Date: 1985-09-01
    Description: Mossbauer spectroscopy has been used to determine the redox equilibria of iron and structure of quenched melts on the composition join Na2Si2O5-Fe2O3 to 40 kbar pressure at 1400° C. The Fe3+/ΣFe decreases with increasing pressure. The ferric iron appears to undergo a gradual coordination transformation from a network-former at 1 bar to a network-modifier at higher (≧10 kbar) pressure. Ferrous iron is a network-modifier in all quenched melts. Reduction of Fe3+ to Fe2+ and coordination transformation of remaining Fe3+ result in depolymerization of the silicate melts (the ratio of nonbridging oxygens per tetrahedral cations, NBO/ T , increases). It is suggested that this pressure-induced depolymerization of iron-bearing silicate liquids results in increasing NBO/ T of the liquidus minerals. Furthermore, this depolymerization results in a more rapid pressure-induced decrease in viscosity and activation energy of viscous flow of iron-bearing silicate melts than would be expected for iron-free silicate melts with similar NBO/ T . ©1985 Springer-Verlag
    Print ISSN: 0342-1791
    Electronic ISSN: 1432-2021
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  • 6
    Publication Date: 1985-03-01
    Description: A general model for the structural state of iron in a variety of silicate and aluminosilicate glass compositions in the systems Na2O-Al2O3-SiO2-Fe-O, CaO-Al2O3-SiO2-Fe-O, and MgO-Al2O3-SiO2-Fe-O is proposed. Quenched melts with variable Al/Si and NBO/ T (average number of nonbridging oxygens per tetrahedrally coordinated cation), synthesized over a range of temperatures and values of oxygen fugacity, are analyzed with57Fe Mössbauer spectroscopy. For oxidized glasses with Fe3+/∑Fe〉0.50, the isomer shift for Fe3+ is in the range ∼0.22–0.33 mm/s and ∼0.36 mm/s at 298 K and 77 K, respectively. These values are indicative of tetrahedrally coordinated Fe3−. This assignment is in agreement with the interpretation of Raman, luminescence, and X-ray, K -edge absorption spectra. The values of the quadrupole splitting are ∼0.90 mm/s (298 K and 77 K) in the Na-aluminosilicate glasses and compare with the values of 1.3 mm/s and 1.5 mm/s for the analogous Ca- and Mg-aluminosilicate compositions. The variations in quadrupole splittings for Fe3+ are due to differences in the degree of distortion of the tetrahedrally coordinated site in each of the systems. The values of the isomer shifts for Fe2+ ions in glasses irrespective of Fe3+/∑Fe are in the range 0.90–1.06 mm/s at 298 K and 1.0–1.15 mm/s at 77 K. The corresponding range of values of the quadrupole splitting is 1.75–2.10 mm/s at 298 K and 2.00–2.35 mm/s at 77 K. The temperature dependence of the hyperfine parameters for Fe2+ is indicative of noninteracting ions, but the values of the isomer shift are intermediate between those values normally attributable to tetrahedrally and octahedrally coordinated Fe2+. The assignment of the isomer-shift values of Fe2+ to octahedral coordination is in agreement with the results of other spectral studies. For reduced glasses (Fe3+/∑Fe≈〈0.50), the value of the isomer shift for Fe3+ at both 298 K and 77 K increases and is linearly correlated with decreasing Fe3+/∑Fe in the range of $$f{O2 } $$ between 10−3 and 10−6 atm when a single quadrupole-split doublet is assumed to represent the absorption due to ferric iron. The increase in value of the isomer shift with decreasing $$f{O2 } $$ is consistent with an increase in the proportion of Fe3+ ions that are octahedrally coordinated. The concentration of octahedral Fe3+ is dependent on the $$T - f{O2 } $$ conditions, and in the range of log $$f{O2 } $$ between 10−2.0 and 10−5 a significant proportion of the iron may occur as iron-rich structural units with stoichiometry similar to that of inverse spinels such as Fe3O4, in addition to isolated Fe2+ and Fe3+ ions. ©1985 Springer-Verlag
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  • 7
    Publication Date: 1985-03-01
    Description: The solubility mechanism of fluorine in quenched SiO2-NaF and SiO2-AlF3 melts has been determined with Raman spectroscopy. In the fluorine abundance range of F/(F+Si) from 0.15 to 0.5, a portion of the fluorine is exchanged with bridging oxygen in the silicate network to form Si-F bonds. In individual SiO4-tetrahedra, one oxygen per silicon is replaced in this manner to form fluorine-bearing silicate complexes in the melt. The proportion of these complexes is nearly linearly correlated with bulk melt F/(F+Si) in the system SiO2-AlF3, but its abundance increases at a lower rate and nonlinearly with increasing F/(F+Si) in the system SiO2-NaF. The process results in the formation of nonbridging oxygen (NBO), resulting in stabilization of Si2O 5 2− units as well as metal (Na+ or Al3+) fluoride complexes in the melts. Sodium fluoride complexes are significantly more stable than those of aluminum fluoride. ©1985 Springer-Verlag
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  • 8
    Publication Date: 2012-02-01
    Description: The crystal structure of chromite FeCr2O4 was investigated to 13.7 GPa and ambient temperature with single-crystal X-ray diffraction techniques. The unit-cell parameter decreases continuously from 8.3832 (5) to 8.2398 (11) Å up to 11.8 GPa. A fit to the Birch–Murnaghan equation of state (EoS) based on the P–V data gives: K 0 = 209 (13) GPa, K ′ = 4.0 (fixed), and V 0 = 588 (1) Å3. The FeO4 tetrahedra and CrO6 octahedra are compressed isotropically with pressure with their Fe–O and Cr–O bond distances decreasing from 1.996 (6) to 1.949 (7) Å and from 1.997 (3) to 1.969 (7) Å, respectively. The tetrahedral site occupied by the Fe2+ cation is more compressible than the octahedral site occupied by the Cr3+ cation. The resulting EoS parameters for the tetrahedral and the octahedral sites are K 0 = 147 (9) GPa, K ′ = 4.0 (fixed), V 0 = 4.07 (1) Å3 and K 0 = 275 (24) GPa, K ′ = 4.0 (fixed), V 0 = 10.42 (2) Å3, respectively. A discontinuous volume change is observed between 11.8 and 12.6 GPa. This change indicates a phase transition from a cubic (space group Fd - $${overline{3}}$$ m ) to a tetragonal structure (space group I 41 /amd ). At the phase transition boundary, the two Cr–O bonds parallel to the c -axis shorten from 1.969 (7) to 1.922 (17) Å and the other four Cr–O bonds parallel to the ab plane elongate from 1.969 (7) to 1.987 (9) Å. This anisotropic deformation of the octahedra leads to tetragonal compression of the unit cell along the c -axis. The angular distortion in the octahedron decreases continuously up to 13.7 GPa, whereas the distortion in the tetrahedron rises dramatically after the phase transition. At the pressure of the phase transition, the tetrahedral bond angles along the c -axis direction of the unit cell begin decreasing from 109.5° to 106.6 (7)°, which generates a “stretched” tetrahedral geometry. It is proposed that the Jahn–Teller effect at the tetrahedrally coordinated Fe2+ cation becomes active with compression and gives rise to the tetrahedral angular distortion, which in turn induces the cubic-to-tetragonal transition. A qualitative molecular orbital model is proposed to explain the origin and nature of the Jahn–Teller effect observed in this structure and its role in the pressure-induced phase transition. ©2011 Springer-Verlag
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  • 9
    Publication Date: 1998-06-23
    Description:  Diopside (CaMgSi2O6) and pseudowollastonite (CaSiO3) have been studied by X-ray powder diffraction and Raman spectroscopy up to their respective melting points. In agreement with previous unit-cell parameters determinations below 1100 K, thermal expansion of diopside along the a and c axis is much smaller than along the b axis. For pseudowollastonite, the axis expansivity increases slightly in the order b 〉 a 〉 c . For both minerals, the change in unit-cell angles is very small and there are no anomalous variations of the other unit-cell parameters near the melting point. With increasing temperatures, the main changes observed in the Raman spectra are strong increases of the linewidths for those bands which mainly represent Si−O−Si bending (near 600 cm−1) or involve Ca−O or Mg−O stretching, in the range 270–500 cm−1 for diopside, and 240–450 cm−1 for pseudowollastonite. At temperatures near the onset of calorimetric premelting effects, this extensive band widening results in a broad Raman feature that can no longer be deconvoluted into its individual components. No significant changes affect the Si−O streching modes. For both diopside and pseudowollastonite, premelting appears to be associated with enhanced dynamics of the alkaline-earth elements. This conclusion contrasts markedly with that drawn for sodium metasilicate in which weaker bonding of sodium allows the silicate framework to distort and deform in such a way as to prefigure the silicate entities present in the melt. ©1998 Springer-Verlag Berlin Heidelberg
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  • 10
    Publication Date: 1985-11-01
    Description: The chemical interaction between fluorine and highly polymerized sodium aluminosilicate melts [Al/(Al+Si)= 0.125–0.250 on the join NaAlO_2-SiO_2] has been studied with Raman spectroscopy. Fluorine is dissolved to form F− ions that are electrically neutralized with Na+ or Al3+. There is no evidence for association of fluorine with either Si4+ or Al3+ in four-fold coordination and no evidence of fluorine in six-fold coordination with Si4+ in these melt compositions. Upon solution of fluorine nonbridging oxygens are formed and are a part of structural units with nonbridging oxygen per tetrahedral cations (NBO/ T ) about 2 and 1. The proportions of these two depolymerized units in the melts increase systematically with increasing F/(F+O) at constant Al/(Al+Si) and with decreasing Al/(Al+Si) at constant F/(F+O). Depolymerization (increasing NBO/ T ) of silicate melts results from a fraction of aluminum and alkalies (in the present study; Na+) reacting to form fluoride complexes. In this process an equivalent amount of Na+ (orginally required for Al-3+charge-balance) or Al3+ (originally required Na+ to exist in tetrahedral coordination) become network-modifiers. The structural data have been used to develop a method for calculating the viscosity of fluorine-bearing sodium aluminosilicate melts at 1 atm. Where experimental viscosity data are available, the calculated and measured values are within 5% of each other. A method is also suggested by which the liquidus phase equilibria of fluorine-bearing aluminosilicate melts may be predicted. In accord with published experimental data it is suggested, for example, that — on the basis of the determined solubility mechanism of fluorine in aluminosilicate melts — with increasing fluorine content of feldspar-quartz systems, the liquidus boundaries between aluminosilicate minerals (e.g., feldspars) and quartz shift away from silica. ©1985 Springer-Verlag
    Print ISSN: 0010-7999
    Electronic ISSN: 1432-0967
    Topics: Geosciences
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