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1.
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   

2.
The Si, Al LII, III and OKα emission and quantum yield spectra were obtained for 24 silicates. It was found that in minerals of a homogeneous anion composition the Si LII, III line has double-humped structure, and when in addition to SiO 4 4? ions of other composition (BeO 4 6? , AlO 4 5? etc.) are present it has triple-humped structure. The process of crystal-glass transition was studied by X-ray spectroscopy. The result is that in spite of the original form of the Si LII, III line of the mineral this line changes its structure in glass and exhibits a typical double-humped structure. The CNDO/2 approach was used to calculate the electronic structure of basic structural groups of silicates from SiO 4 4? to Si5O 16 12? by replacing one or two of the Si atoms by Be, B, Al and P. A qualitative interpretation of the X-ray spectra is presented.  相似文献   

3.
Experiments on the join Al2SiO5-“Mn2SiO5” of the system Al2O3-SiO2-MnO-MnO2 in the pressure/temperature range 10–20 kb/900–1050° C with gem quality andalusite, Mn2O3, and high purity SiO2 as starting materials and using /O2-buffer techniques to preserve the Mn3+ oxidation state had following results: At 20 kb/1000°C orange-yellow kyanite mixed crystals are formed. The kyanite solid solubility is limited at about (Al1.88Mn 0.12 3+ )SiO5 and, thus, equals approximately that on the join Al2SiO5-“Fe2SiO5” (Langer and Frentrup, 1973) indicating that there is no Jahn-Teller stabilisation of Mn3+ in the kyanite matrix. 5 mole % substitution causes the kyanite lattice constants a o, b o, c o, and V o to increase by 0.015, 0.009, 0.014 Å, and 1.6 Å3, resp., while α, β, γ, remain unchanged. Between 10 and 18 kb/900°C, Mn3+-substituted, strongly pleochroitic (emeraldgreen-yellow) andalusitess (viridine) was obtained. At 15 kb/900°C, the viridine compositional range is about (Al1.86Mn 0.14 3+ )SiO5-(Al1.56Mn 0,44 3+ )SiO5. Thus, Al→Mn3+ substitutional degrees are appreciably higher in andalusite than in kyanite, proving a strong Jahn-Teller effect of Mn3+ in the andalusite structure, which stabilises this structure type at the expense of kyanite and sillimanite and, thus, enlarges its PT-stability range extremely. 17 mole % substitution cause the andalusite constants a o, b o, c o, and V o to increase by 0.118, 0.029, 0.047 Å and 9.4 Å3, resp. At “Mn2SiO5”-contents smaller than about 7 mole %, viridine coexists with Mn-poor kyanite. At “Mn2SiO5”-concentrations higher than the maximum kyanite or viridine miscibility, braunite (tetragonal, ideal formula Mn2+Mn3+[O8/Si04]), pyrolusite and SiO2 were found to coexist with the Mn3+-saturated ky ss or and ss, respectively. In both cases, braunites were Al-substituted (about 1 Al for 1 Mn3+). Pure synthetic braunites had the lattice constants a o 9.425, c o, 18.700 Å, V o 1661.1 Å3 (ideal compn.) and a o 9.374, c o 18.593 Å3, V o 1633.6 Å3 (1 Al for 1 Mn3+). Stable coexistence of the Mn2+-bearing phase braunite with the Mn4+-bearing phase pyrolusite was proved by runs in the limiting system MnO-MnO2-SiO2.  相似文献   

4.
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   

5.
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   

6.
Graphite forms crystals up to 0.08 mm in size in carbonates or argillaceous carbonates directly under- and overlying black shale. Increased contents of Si, Al, Ca, and K in graphite are related to intercalations of graphite-montmorillonite and less to intercalations of graphite-illite. Quartz and gibbsite are also detected. The formation of graphite was probably a two-stage process:
  1. Catalytic oxidation of organic matter. As a result of oxidation original organic matter has been enriched as aromatic hydrocarbons (benzene ring compounds) being most resistant to oxidation.
  2. Ordering of conjugated benzene rings on the 001 montmorillonite plane as a matrix. As a result, the c0 of dry montmorillonite increased to 1.678±0.020 or 2.450±0.050 nm. Primary layers of graphite became themselves matrices for the next layers of conjugated rings producing microscopically visible graphite.
To a less extent the process of dehydrogenesis and conjugation of aromatic rings took place in a reaction with Al, Si, and OH of phyllosilicates producing Al(OH)3 (gibbsite), former H4SiO4 (now quartz), and H2O.  相似文献   

7.
Ti-andradites were synthesized at a pressure of P(H2O)=3 kbar and temperatures of 700–800° C. Oxygen fugacities were controlled by solid state buffers (Ni/NiO; SiO2 + Fe/Fe2SiO4). The Fe2+-and Fe3+-distribution was determined by low temperature Mössbauer spectroscopy. The water content was measured by a solid's moisture analyzer. The chemical composition of the synthetic and the natural sample has been determined by electron microprobe. Ti-andradites from runs at high oxygen fugacities have Fe3+ on octahedral and tetrahedral sites; Ti-andradites from runs at low oxygen fugacities have tetrahedrally and octahedrally coordinated Fe2+ as well. These “reduced” garnets must also contain Ti3+ on octahedral sites. Charge balance is maintained due to substitution of O2? by (OH)? by two mechanisms: (SiO4)4? ? (O4H4)4? and (Fe3+O6)9? ? (Fe2+O5OH)9?. FTIR spectra of the synthetic samples do show the presence of structurally bound (OH)?. In a natural sample tetrahedrally and octahedrally coordinated Fe3+ are observed together with Fe2+ on all three cation sites of the garnet structure.  相似文献   

8.
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   

9.
The first silicate possessing a K2NiF4-type structure (Ca2SiO4) has been synthesized at loading pressures between 220 and 260 kbar and a temperature of about 1000° C in a diamond-anvil press coupled with a YAG laser heater. The lattice parameters for Ca2SiO4 (K2NiF4-type) area=3.564±0.002 andc=11.66±0.01 Å at room temperature and 1 bar pressure, and the molar volume is 44.57±0.05 cm3. The lattice parameter for the non-quenchable high-pressure perovskite modification of CaSiO3 is estimated to be 3.56±0.03 Å at STP conditions. To date, A2BX4 compounds possessing the K2NiF4-type structure arein all cases less dense than their corresponding mixtures of ABX3 and AX compounds possessing, respectively, the perovskite (or related structures) and rocksalt structures. Hence the K2NiF4 structure is unstable relative to the mixture perovskite plus rocksalt at high pressures. For example, in a preliminary experimental study Ca2GeO4 in the K2NiF4-type structure has been found to transform to an as-yet-undetermined phase or assemblage at pressures between 200 and 250 kbar and at about 1000° C. It is concluded that a similar phase transformation might also occur in Ca2SiO4 (K2NiF4 type) but that the K2NiF4-type structure would not be adopted by Mg2SiO4 in the earth's mantle.  相似文献   

10.
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   

11.
Subsolidus phase relations on the join CaMgSi2O6-CaFe3+ AlSiO6-CaTiAl2O6 were studied by the ordinary quenching method at \(f_{O_2 } = 10^{ - 11} \) atm and 1,100°C. Crystalline phases encountered are clinopyroxeness (ss:solid solution) (Cpxss), melilite (Mel), perovskite (Pv), spinelss (Spss), magnetitess (Mtss) and anorthite (An). There is no Cpxss single phase field, and the following assemblages were found; Cpxss+Mel, Cpxss+Mel+Spss, Cpxss+Mel+Pv, Cpxss+Mel+Spss+Pv, Cpxss+Pv+Spss+An, Spss+Pv+Mel+An+Cpxss, Mel+Mtss+An+Spss+Cpxss+liquid and Mel+Mtss+An+Spss+Cpxss+Pv. Mössbauer spectral study revealed that Cpxss contains both Fe2+ and Fe3+ in the octahedral site, and it was confirmed that the CaFe3+ AlSiO6 content in the Cpxss at low \(f_{O_2 } \) is considerably less than that in the Cpxss crystallized in air, whereas the CaFe2+Si2O6 component increases. The maximum solubility of CaTlAl2O6 component in the Cpxss at low \(f_{O_2 } \) is higher than that in air. The decrease of CaFe3+ AlSiO6 in the Cpxss at low \(f_{O_2 } \) may cause increase of CaTial2O6 in the Cpxss.  相似文献   

12.
Single crystals of ferromagnesian orthosilicates with modified spinel (β) and spinel (γ) structure as large as 500 μm have been grown by solid state crystallization at high temperature and high pressure using an MA8-type apparatus driven in a 2,000-ton uniaxial press. This system is capable of generating pressures of 24.0 (±0.3) GPa at 2,400 (±50)°C for one hour in a sample assembly volume of 0.14 cm3. Crystals larger than 100 μm were observed to grow only at pressures within 5 percent of the phase boundary between the stability fields of the β and γ phases. Experimental determination of the phase boundaries between β or β+γ and γ phases for (Mg,Fe)2SiO4 has been extended to 22 GPa and 2,400°C. The effect of configurational entropy due to disordering is evaluated to be minimal on the basis of the cationic distribution in the synthesized samples; thus, we conclude that the phase boundary between β or β+γ and γ phases remains essentially linear to 2,400°C. In (Mg,Fe)2SiO4 solid solutions, the stability field of the γ phase shifts towards the lower pressures with increasing iron content at a rate of a 1 GPa for each 10 mole percent Fe. Assignment of the β→β+γ→γ transition to the seismic 550 km discontinuity is rejected by the present phase diagram results for (Mg0.9Fe0.1)2SiO4 and measurement of acoustic velocities for β and γ Mg2SiO4, but the discontinuity may be caused by a phase transition of pyroxene to a garnet-like structure.  相似文献   

13.
Nanohybrid of graphene oxide (GO) and azide-modified Fe3O4 nanoparticles (NPs) were fabricated using click reaction. First, Fe3O4 NPs were modified by 3-azidopropionic acid. Then, click-coupling of azide-modified Fe3O4 NPs with alkyne-functionalized GO was carried out in the presence of CuSO4·5H2O and sodium l-ascorbate at room temperature. The attachment of Fe3O4 NPs onto the graphene nanosheets was confirmed by Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy, thermogravimetric analysis, energy dispersive X-ray spectrometry and X-ray diffraction spectrometry. As the FTIR spectroscopy and energy dispersive X-ray spectrometry analysis showed, the final magnetic graphene nanosheets were also reduced by sodium ascorbate which is a merit for click-coupling reactions. The specific saturation magnetization of the Fe3O4-clicked GO was 44.3 emu g?1. The synthesized hybrid was used in the adsorption of methylene blue and congo red (CR). The adsorption capacities in the studied concentration range were 109.5 and 98.8 mg g?1 for methylene blue and CR, respectively.  相似文献   

14.
This paper presents the point-defect thermodynamics for fayalite and olivine solid solutions (Fe x Mg1?x )2SiO4. By means of thermogravimetry, the metal-to-oxygen ratio of these silicates has been determined as a function of oxygen potential, compositionx and temperature. Experiments were performed in the range of 1,000° C≦T≦1,280° C and 0.2≦x≦1.0. It is found that V Me ″ , Fe Me · and the associate {Fe′ Si ′ Fe Me · } are the majority defects. With this knowledge it is possible to calculate the nonstoichiometry at given temperature as a function of \(p_{O_2 } \) and \(a_{SiO_2 } \) . The cation vacancy concentration shows a \(p_{O_2 }^{1/5} \) -dependence (forx≧0.2) and increases at givenT and \(p_{O_2 } \) almost exponentially with compositionx. In the composition range studied here, the silicates show an oxygen excess, and FeO is more soluble in the olivine than SiO2.  相似文献   

15.
Infrared (IR) and Raman spectroscopic methods are important complementary techniques in structural studies of aluminosilicate glasses. Both techniques are sensitive to small-scale (<15 Å) structural features that amount to units of several SiO4 tetrahedra. Application of IR spectroscopy has, however, been limited by the more complex nature of the IR spectrum compared with the Raman spectrum, particularly at higher frequencies (1200–800 cm?1) where strong antisymmetric Si-O and Si-O-Si absorptions predominate in the former. At lower frequencies, IR spectra contain bands that have substantial contributions from ‘cage-like’ motions of cations in their oxygen co-ordination polyhedra. In aluminosilicates these bands can provide information on the structural environment of Al that is not obtainable directly from Raman studies. A middle frequency envelope centred near 700 cm?1 is indicative of network-substituted AlO4 polyhedra in glasses with Al/(Al+Si)>0·25 and a band at 520–620cm?1 is shown to be associated with AlO6 polyhedra in both crystals and glasses. The IR spectra of melilite and melilite-analogue glasses and crystals show various degrees of band localization that correlate with the extent of Al, Si tetrahedral site ordering. An important conclusion is that differences in Al, Si ordering may lead to very different vibrational spectra in crystals and glasses of otherwise gross chemical similarity.  相似文献   

16.
Most of the Al3+ entering the pyroxenes does so by substituting for tetrahedral Si4+. This creates a charge imbalance that requires the simultaneous entry of Cr3+, Ti4+, Fe3+ or Al3+ into octahedral sites. Cr3+, because of its high crystal field stabilisation energy (CFSE), is the most important of these elements to enter the early-formed pyrosenes but it is replaced by Ti4+ later in fractionation when the Cr3+ content of the melt becomes depleted. The dependence of Cr3+ and Ti4+ on charge balance controls their partition between coexisting pyroxenes and olivines. Ca-rich pyroxene which contains more Al3+ than Ca-poor pyroxene also has more Ti4+ and Cr3+ whereas olivine, which contains negligible Al3+, has low Cr3+ and Ti4+. The Al3+ content of pyroxenes is influenced by changes in P, T, \(a_{{\text{SiO}}_{\text{2}} }\) and \(a_{{\text{Al}}_{\text{2}} {\text{O}}_{\text{3}} }\) of the magma and by the nature of the ion providing charge balance in the octahedral site. Of these \(a_{{\text{SiO}}_{\text{2}} }\) is dominant and variations in the Al3+ content of the Jimberlana pyroxenes correspond closely with the expected changes in the \(a_{{\text{SiO}}_{\text{2}} }\) of the melt. The substitution of divalent ions, such as Mn2+ and Ni2+, in the pyroxene lattice is by replacement of Fe2+ or Mg2+ in the octahedral M 3 and M 2 sites and is therefore independent of charge balance. If there are no size restrictions, the principal factor to be considered is the CFSE the ion receives in octahedral co-ordination. Ni2+, which receives a high CFSE, partitions strongly between the early-formed pyroxenes and olivines and therefore becomes depleted in the magma with fractionation. Conversely Mn2+, which receives zero CFSE, concentrates in the magma with fractionation and becomes a more important substitute in the later-formed pyroxenes. Its geochemical behaviour is controlled by its size. The narrow miscibility gap of the Jimberlana pyroxenes and the high En content of the Ca-poor pyroxenes at the bronzite pigeonite changeover suggest that these pyroxenes crystallised at a higher temperature than pyroxenes of comparable composition from other intrusions.  相似文献   

17.
With increasing pressure, MnSiO3 rhodonite stable at atmospheric pressure transforms to pyroxmangite, then to clinopyroxene and further to tetragonal garnet, which finally decomposes into MnO (rocksalt) plus SiO2 (stishovite). High temperature solution calorimetry of synthetic rhodonite, clinopyroxene and garnet forms of MnSiO3 was used to measure the enthalpies of these transitions. ΔH 974 0 for the rhodonite-clinopyroxene and ΔH 298 0 for the clinopyroxene-garnet transition are 520±490 and 8,270±590 cal/mol, respectively. The published data on the enthalpy of the rhodonite-pyroxmangite transition, phase equilibrium boundaries, compressibility and thermal expansion data are used to calculate entropy changes for the transitions. The enthalpy, entropy and volume changes are very small for all the transitions among rhodonite, pyroxmangite and clinopyroxene. The calculated boundary for the clinopyroxene-garnet transition is consistent with the published experimental results. The pyroxene-garnet transition in several materials, including MnSiO3, is characterized by a relatively small negative entropy change and large volume decrease, resulting in a small positiveP – T slope. The disproportionation of MnSiO3 garnet to MnO plus stishovite and of Mn2SiO4 olivine to garnet plus MnO are calculated to occur at about 17–18 and 14–15 GPa, respectively, at 1,000–1,500 K.  相似文献   

18.
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   

19.
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   

20.
Based on the expert review of literature data on the thermodynamic properties of species in the Cl-Pd system, stepwise and overall stability constants are recommended for species of the composition [PdCl n ]2 ? n , and the standard electrode potential of the half-cell PdCl 4 2? /Pd(c) is evaluated at E 298,15° = 0.646 ± 0.007 V, which corresponds to Δ f G 298.15° = ?400.4 ± 1.4 kJ/mol for the ion PdCl 4 2? (aq). Derived from calorimetric data, Δ f H 298.15° PdCl 4 2? (aq) = ?524.6 ± 1.6 kJ/mol and Δ f H 298.15° Pd2+(aq) = 189.7 ± 2.6 kJ/mol. The assumed values of the overall stability constant of the PdCl 4 2? ion and the standard electrode potential of the PdCl 4 2? /Pd(c) half-cell correspond to Δ f G 298.15° = 190.1 ± 1.4 kJ/mol and S 298.15° = ?94.2 ± 10 J/(mol K) for the Pd2+(aq) ion.  相似文献   

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