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1.
The effects of the addition of Al2O3 on the large stable two liquid field in the SiO2-TiO2-CaO-MgO-FeO system were experimentally determined. The increase of Al2O3 content in the starting composition results in the decrease of critical temperature, phase separation and liquidus temperature of the two liquid field until it is rendered completely metastable. The shrinkage of the two liquid field indicates that Al2O3 is acting in the role of a network former and homogenizes the structure of the two melts. In this alkali-free system Al+3 utilizes the divalent cations, Ca+2 and Mg+2, for local charge balance with a preference for Ca+2 over Mg+2. Thus, AlO4 tetrahedra combine with SiO4 tetrahedra to form an aluminosilicate framework which polymerizes the SiO2-poor melt and makes it structurally more similar to the SiO2-rich melt. However, Ca+2 and Mg+2 are not as efficient in a charge balancing capacity as the monovalent K+ and Na+ cations. The lack of alkalis in this system limits the stability of AlO4 tetrahedra in the highly polymerized SiO2-rich melt and results in the preference of Al2O3 for the SiO2-poor melt. The partitioning systematics of Ti are virtually identical to those of Al. It is concluded that Ti occurs in tetrahedral coordination as a network forming species in both the high — and low — SiO immiscible melts. 相似文献
2.
B. Marler 《Physics and Chemistry of Minerals》1988,16(3):286-290
Five different refraction formulas were applied to SiO2 polymorphs in order to determine the most suitable refractive index-density relation. 13 SiO2 polymorphs with topological different tetrahedral frameworks are used in this study including eight new low density SiO2 polymorphs — so called “guest free porosils”. These SiO2 polymorphs cover a density range from 1.76 to 2.92 g/cm3. The mean refractive indices (ovn) of the porosils have been determined by the immersion method, the densities (ρ) were calculated from the unit cell parameters. Assuming the polarizability (α) of all SiO2 polymorphs to be constant the general refractivity formula $$\{ 2\overline {11} 0\} \langle 0001\rangle $$ turned out to be the most suitable for SiO2 polymorphs. Regression analysis yields an electronic overlap parameter b=1.2(1). 相似文献
3.
Infrared absorption spectra of the high-pressure polymorphs β-Mg2SiO4 and β-Co2SiO4 have been measured between 0 and 27 GPa at room temperature. Grüneisen parameters determined for 11 modes of β-Mg2SiO4 (frequencies of 300 to 1,050 cm?1) and 5 modes of β-Co2SiO4 (490 to 1,050 cm?1) range between 0.8 and 1.9. Averaging the mid-infrared spectroscopic data for β-Mg2SiO4 yields an average Grüneisen parameter of 1.3 (±0.1), in good agreement with the high-temperature thermodynamic value of 1.35. Similarly, we find a value of 1.05 (±0.2) for the average spectroscopic Grüneisen parameter of β-Co2SiO4. 相似文献
4.
G. Will L. Cemič E. Hinze K. -F. Seifert R. Voigt 《Physics and Chemistry of Minerals》1979,4(2):189-197
Electrical conductivities of Ni2SiO4, Fe2SiO4, and MgSiO3 were measured on synthetic powders in the temperature range 340° to 1,100° C and at pressures up to 20 kbars. For ternary compounds such as olivines and pyroxenes the control of two further variables, like the chemical activities of two components are needed, besides temperature and pressure. The activities of the corresponding binary oxides were controlled by equilibrating the samples with their neighbour-phases. Control of the oxygen partial pressure was achieved by buffer techniques. From the slopes of the lg σ vs. 1/T lines the activation energies were calculated for 10 kbar: 0.56 eV and 2.7 eV for Ni2SiO4 in equilibrium with SiO2 and Ni/NiO-buffer for the temperature range 500°–800°C and 800°–1,000°C resp. 0.52 eV for Fe2SiO4 in equilibrium with SiO2 and metallic iron, and 0.38 eV in equilibrium with SiO2 and magnetite; 1.11 eV for MgSiO3 in equilibrium with SiO2, and 1.25 eV in equilibrium with Mg2SiO4. 相似文献
5.
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 ofnonbridging 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. 相似文献
6.
Takamitsu Yamanaka 《Physics and Chemistry of Minerals》1986,13(4):227-232
X-ray structure refinements of Ni2SiO4 and Fe2SiO4 spinels have been made as a function of temperature and heating duration by intensity measurements at high temperatures and room pressure. The lattice parameters of Ni2SiO4 spinel linearly increased with temperature up to 1,000° C. However, Fe2SiO4 spinel exhibited a nonlinear thermal expansion and was converted to a polycrystalline mixture of spinel and olivine by heating of less than one-hour at 800° C. The ratios between the octahedral and tetrahedral bond lengths D oct/D tetr and between the shared and unshared edge distances (O-O)sh/(O-O)unsh in Fe2SiO4 spinel were both much larger than those in Ni2SiO4. These ratios increase with temperature. The Fe2SiO4 spinel more readily approached a activation state which facilitated the transition to the olivine structure than the Ni2SiO4 spinel. The lattice parameter of Ni2SiO4 spinel decreased with heating period at constant temperatures of 700° C and 800° C. The parameter of the quenched sample after heating for 52 h at 700° C was smaller than that of the nonheated sample. The refinements of the site occupancies at each heating duration indicated an increase in the cation deficiency in both tetrahedral and octahedral sites. Electron microprobe analysis, however, proved no significant difference in the chemical compositions between the quenched and nonheated samples. Si and Ni atoms displaced from normally occupied spinel lattice sites are assumed to settle in vacant sites defined by the cubic close packed oxygen sublattice in a manner which preserves the electric neutrality of the bulk crystal. 相似文献
7.
The decomposition of fayalite (Fe2SiO4) in oxygen potential gradients is studied at T=1,418 K. The compound will be decomposed into its component oxides wüstite, Fe1?δO, and silica, SiO2, by the simultaneous action of two different oxygen partial pressures, exceeding a critical ratio, despite the fact that fayalite is stable at both the lower and the higher oxygen potential. A quantitative analysis of the decomposition process caused by defect fluxes within the bulk Fe2SiO4 is given. 相似文献
8.
Calcium-olivine, γ-Ca2SiO4, larnite, β-Ca2SiO4, merwinite, Ca3Mg(SiO4)2, and monticellite, CaMgSiO4, are considered. According to a rigid oxyanion scheme, eulerian orientation angles of the SiO4 tetrahedra and translation coordinates of Ca and Si atoms are specified as structural variables τk. All derivatives of the static energy (Born model) contain atomic charges and repulsive parameters as unknowns; the minimum energy conditions ?E L/?τk=0 yield 34 equations which are solved by a least-squares method. The set of energy parameters fitting structural properties of all four phases together is: z Ca=1.50, z o=?1.10 e, r Ca=1.05, ρ=0.25 Å; the Mg charge was fixed at 1.38 e, from a previous study on forsterite. An average shift of 0.04 Å is observed between experimental and least-energy calculated atomic positions. Results are compared with those of Mg2SiO4, where the fit was based both on thermoelastic and on structural properties. If no charge values were fixed “a priori”, just ratios between charges could be determined by fitting them to structural data only. 相似文献
9.
Raymond Jeanloz 《Physics and Chemistry of Minerals》1980,5(4):327-341
Infrared (IR) absorption spectra are presented for olivine (α) and spinel (γ) phases of A2SiO4 (A=Fe, Ni, Co) and Mg2GeO4. IR spectra of β phase (“modified spinel”) Co2SiO4 and of α Mg2SiO4 are also included. These results provide reference spectra for the identification of olivine high-pressure polymorphs. Isostructural and isochemical correlations are used to support a general interpretation of the spectra and to predict the spectrum of γ Mg2SiO4. A γ Mg2GeO4 sample equilibrated at 1,000° C shows evidence of partial inversion, but one equilibrated at 730° C does not. This suggests that partial inversion could occur in silicate spinels at elevated temperatures and pressures, however no evidence of inversion is seen in the ir spectra of the silicates in this study. 相似文献
10.
Michele Catti 《Physics and Chemistry of Minerals》1981,7(1):20-25
In the lattice energy expression of forsterite, based on a Born-Mayer (electrostatic+repulsive+dispersive) potential, the oxygen charge z o, the hardness parameter ρ and the repulsive radii r Mg and r Si appear as unknown parameters. These were determined by calculating the first and second partial derivatives of the energy with respect to the cell edges, and equalizing them to quantities related to the crystal elastic constants; the overdetermined system of equations was solved numerically, minimizing the root-mean-square deviation. To test the results obtained, the SiO 4 4? ion was assumed to move in the unit-cell, and the least-energy configuration was sought and compared with the experimental one. By combining the two methods, the optimum set of parameters was: z o=?1.34, ρ=0.27 Å, r Mg=0.72 Å, r Si=0.64 Å. The values ?8565.12 and ?8927.28 kJ mol?1 were obtained, respectively, for the lattice energy E Land for its ionic component E L 0 ,which accounts for interactions between Mg2+ and SiO 4 4? ions only. The charge distribution calculated on the SiO 4 4? ion was discussed and compared with other results. Using appropriate thermochemical cycles, the formation enthalpy and the binding energy of SiO 4 4? were estimated to be: ΔH f(SiO 4 4? )=2117.6 and E(SiO 4 4? )=708.6 kJ mol?1, respectively. 相似文献
11.
The crystal structure of perovskite-type MgSiO3 has been studied up to 96 kbar, using a miniature diamondanvil pressure cell and by means of single-crystal four-circle diffractometry. The observed unit cell compression gives a bulk modulus of K o=2.47 Mbar, assuming K′o=4. The unit cell compression is controlled mainly by the tilting of SiO6 octahedra. The effect of pressure is to change Mg polyhedron towards 8-fold coordination rather than 12-fold coordination. The polyhedral bulk moduli of SiO6 and MgO8 are 3.8 Mbar and 1.9 Mbar, respectively. 相似文献
12.
Enthalpies of solution in molten 2 PbO · B2O3 at 974 K were measured for four spinelloids, phases I (0.75 NiAl2O4 · 0.25 Ni2SiO4), II (0.60 NiAl2O4 · 0.40 Ni2SiO4), III and IV (0.50 NiAl2O4 · 0.50 Ni2SiO4) in the system NiAl2O4 · Ni2SiO4. The enthalpies (in cal per 4-oxygen mol) of formation from NiAl2O4 and Ni2SiO4 spinels are: phase I, 945±366; phase II, 1072±360; phase III, 2253±390; phase IV, 3565±544. Using these enthalpy data in combination with phase relations at high pressure at 1373 K, positive entropies of formation of the spinelloids from NiAl2O4 and Ni2SiO4 spinels were estimated (in cal mol?1 K?1): phase I, 1.2; phase II, 1.5; phase III, 2.0–2.3; phase IV, 3.0–3.1. The thermochemical data obtained above suggest that the spinelloids are “entropy-stabilized” phases with partially disordered cation distributions. The configurational entropies of the spinelloids were calculated based on the observed cation distribution in each spinelloid phase. The positive entropies of formation of the spinelloids from the spinel endmembers are due primarily to the configurational entropies although small positive vibrational entropy changes may also exist. 相似文献
13.
14.
Crystal field stabilization (CFS) plays a significant role in determining equilibrium phase boundaries in olivine→spinel transformations involving transition-metal cations, including Fe2+ which is a major constituent of the upper mantle. Previous calculations for Fe2SiO4 ignored pressure and temperature dependencies of crystal field stabilization enthalpies (CFSE) and the electronic configurational entropy (S CFS). We have calculated free energy changes (ΔG CFS) due to differences of crystal field splittings between Fe2SiO4 spinel and fayalite from: ΔG CFS=?ΔCFSE?TΔS CFS, as functions of P and T, for different energy splittings of t 2g orbital levels of Fe2+ in spinel. The results indicate that ΔG CFS is always negative, suggesting that CFS always promotes the olivine→spinel transition in Fe2SiO4, and expands the stability field of spinel at the expense of olivine. Because of crystal field effects, transition pressures for olivine→spinel transformations in compositions (Mg1?x Fe x )2SiO4 are lowered by approximately 50x kbar, which is equivalent to having raised the olivine→spinel boundary in the upper mantle by about 15 km. 相似文献
15.
Quentin Williams Paul McMillan Thomas F. Cooney 《Physics and Chemistry of Minerals》1989,16(4):352-359
The vibrational frequencies of a series of splatquenched, olivine glasses spanning the compositional range from Mg2SiO4 to Mn2SiO4 have been determined using both infrared and Raman spectroscopies. The spectra of all glasses show evidence of tetrahedral coordination of silicon (possibly with some slight distortions), and largely octahedral coordination of magnesium. Spectra of Mn-rich glasses indicate that there is some manganese in 4 or 5-fold coordination. The frequencies observed for the fundamental vibrations of the silica tetrahedra are similar to those previously observed for SiO4 groups in both crystalline and glassy orthosilicates. Additionally, there is evidence for a small amount of silicate polymerization in all glasses characterized: vibrations attributable to Si2O7 groups are visible in both infrared and Raman spectra. 相似文献
16.
Shock-recovery experiments have been carried out on andalusite single crystals of gem quality in a pressure range from 300 up to 575 kbar. Infrared spectroscopic investigations indicate a progressive shock-induced transformation of andalusite into short-range-ordered Al2O3 and SiO2 phases within a pressure interval from ~360 to ~575 kbar. Exposure to dynamic pressures of about 575 kbar results in andalusite breaking down into incoherently crystallized γ-Al2O3, well-crystallized α-Al2O3 and X-ray amorphous SiO2. The shock disproportionation of andalusite is presumed to take place in three separate stages of reaction. The comparison of shock-induced reactions with results from static experiments on kyanite indicates significant differences in the transformation pressures and in the mechanism of the high pressure decomposition. 相似文献
17.
C. A. Angell C. A. Scamehorn C. C. Phifer R. R. Kaiyala P. A. Cheeseman 《Physics and Chemistry of Minerals》1988,15(3):221-227
We give a brief review of ion dynamics studies of liquid and glassy states of SiO2 and silicate colutions which have been carried out in recent years in this laboratory. We summarize studies on SiO2, Na+ migration in Na2O·SiO2 in the “glassy state”, and ionic coordination in multicomponent framework silicates. We present new results on the coordination of Al3+ in albite as a function of pressure and show that it is consistent with results of laboratory studies on albite glasses formed at high pressure. We compare calculated PVT data for jadeite, albite and diopside and relate the behavior of the low pressure compressibility to the spinodal limit at negative pressures. Some preliminary studies of inert gas solution in jadeite and of CO2 solution in a glass having a composition of approximately Na2O·3SiO2 are described. 相似文献
18.
The possibilities of exoelectron spectroscopy to investigate defects in dielectrics are demonstrated for phenakite Be2SiO4, its structural analogs Zn2 SiO4, Be2GeO4, solid solutions Be2Si1?x Ge x O4 (x=0÷1) and α-quartz. Emission maxima at 330 and 670 K in phenakite have been found to be due to [GeO4]5? andE' centers, respectively. Structural disturbances in the silicon and oxygen positions have been shown to control the exoemission activity of the crystals. Radiation induced decrease of exoemission activity connected with generation ofE' centers by neutron irradiation has been discovered. The energy level scheme of active centers in the subsurface region of Be2SiO4 has been established. 相似文献
19.
Seven clinopyroxenes in the system CaScAlSiO6- CaAl2SiO6 synthesized at 1 atm and under high pressure have been studied by Raman spectroscopy. The T-O-T stretching band of CaScAlSiO6 pyroxene can be deconvoluted into three bands corresponding to Al-O-Al, Al-O-Si, and Si-O-Si stretching vibrations, although that of CaAl2SiO6 can be deconvoluted into the two bands (Al-O-Al+Al-O-Si) and Si-O-Si. The Al-O-Si Raman shifts of CaScAlSiO6 and CaAl2SiO6 pyroxenes are found to fall on the linear plot of the relationship between T-T distance and Raman shifts in ABSi2O6-type pyroxenes, suggesting that the Al-O-Si chains are relatively long. Variation of areal fractions of the Raman bands demonstrates that the partial disordering of Al/Si depends on the ionic radius and electronegativity of the octahedral ion. 相似文献
20.
The amorphous phase of SiO2 produced upon recovery of shock-compressed quartz demonstrates a wide range of refractive indices which can be correlated to the shock state. Both infra-red absorption spectra and X-ray diffraction patterns indicate that the shock-produced amorphous SiO2 has a statistically more-random atomic distribution and longer Si-O and shorter Si-Si separation than does fused silica. By accounting for phase transformation, the calculated values of the shock and residual temperature are much higher than those obtained by Wackerle (1962) to a pressure of 700 kbar. Our results are consistent with experimental ones. 相似文献