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1.
The dielectric constants and dielectric loss values of 4 Ca-containing minerals were determined at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: vesuvianitel κ′ a=9.93 tan δ=0.006 κ′ c=9.79 tan δ=0.005 vesuvianitel κ′ a=10.02 tan δ=0.002 κ′ c=9.85 tan δ=0.003 zoisite1 κ′ a =10.49 tan δ=0.0006 κ′ b =15.31 tan δ=0.0008 κ′ c=9.51 tan δ=0.0008 zoisite2 κ′ a =10.55 tan δ=0.0011 κ′ b =15.45 tan δ=0.0013 κ′ c=9.39 tan δ=0.0008 epidote κ′ 11= 9.52 tan δ=0.0008 κ′ 22=17.1 tan δ=0.0009 κ′ 33= 9.37 tan δ=0.0006 fluorapatite1 κ′ a =10.48 tan δ=0.0008 κ′ c = 8.72 tan δ=0.0114 fluorapatite2 κ′ a =10.40 tan δ=0.0010 κ′ c=8.26 tan δ=0.0178 The deviation (δ) between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to α D (mineral)=∑ α D (oxides) for vesuvianite is ～ 0.5%. The large deviations of epidote and zoisite from the additivity rule with Δ=+ 10.1 and + 11.7%, respectively, are attributed to “rattling” Ca ions. The combined effects of both a large F thermal parameter and possible F-ion conductivity in fluorapatite are believed to be responsible for Δ=+2–3%. Although variation of oxygen polarizability with oxygen molar volume (Vo) is believed to affect the total polarizabilities, the variation of Vo in these Ca minerals is too small to observe the effect.  相似文献   

2.
The dielectric constants and dissipation factors of topaz, scapolite and orthoclase were determined at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: topaz κ′ a =6.61 tan δ=0.0005 κ′ b =6.82 tan δ=0.0007 κ′ c =6.81 tan δ=0.0007 orthoclase κ′ a =4.69 tan δ=0.0007 κ′ b =5.79 tan δ=0.0007 κ′ c =5.63 tan δ=0.0011 κ′ 11 =4.72 κ′ 22 =5.79 κ′ 33 =5.76 scapolite κ′ a =6.74 tan δ=0.0004 κ′ c =8.51 tan δ=0.0004 The deviation (Δ) between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of ion polarizabilities according to α D (mineral)=∑αD (ions) for topaz is 2.5%. The large deviations of orthoclase and scapolite from the oxide additivity rule with δ=+7.2 and + 17.6%, respectively, are attributed to “rattling” K ions in orthoclase and “rattling” (Na,K,Ca) ions and disordered O= and Cl- ions in scapolite.  相似文献   

3.
Using fused SiO2, CaF2, and SrF2 samples with accurately known dielectric constants, we have evaluated the accuracy and precision of two-terminal dielectric constant measurements on small single crystals using empirically determined edge corrections. Values of κ′ at 1 MHz of 3.836±0.05 for silica, 6.814±0.07 for CaF2 and 6.463±0.09 for SrF2 indicate an accuracy and precision of 1.0–1.5% for samples having areas of 0.05–1.0 cm2. Dielectric constants of BeO, MgO, and CaO measured by this technique are: BeO, κ′a=6.87 and κ′c=7.74; MgO, κ′= 9.90; and CaO, κ′=11.95 where κ′a and κ′c are the dielectric constants parallel to the a and c axes, respectively. Dielectric loss measurements on CaO in vacuum between 5–400 K at 10–105 Hz indicate significant dispersion at temperatures higher than 300 K, but the effect of the losses on the dielectric constant is less than 1% at 1 MHz and 300 K.  相似文献   

4.
The dielectric constants and dissipation factors of LiAlSi2O6, CaAl2Si2O8 and CaMgSi2O6 in both the crystalline (α-spodumene, anorthite, and diopside) and amorphous forms were determined at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: spodumene κ′ 11=7.30 tan δ= 0.0007 κ′22=8.463 tan δ= 0.0002 κ′33 =11.12 tan δ= 0.0007 anorthite κ′ a *=5.47 tan δ= 0.0009 κ′b *=8.76 tan δ= 0.0010 κ′c *=7.19 tan δ= 0.0013 diopside κ′11=9.69 tan δ= 0.0016 κ′22 = 7.31 tan δ= 0.0007 κ′33=7.29 tan δ= 0.00019 LiAlSi2O6 κ′=8.07 tan δ= 0.047 amorphous CaAl2Si2O8 κ′=7.50 tan δ= 0.0024 amorphous CaMgSi2O6 κ′=8.89 tan δ= 0.0021 amorphous The dielectric properties of a spodumene glass, progressively crystallized at different conditions, were also determined. As the crystallization temperature was increased from 720 to 920° C, κ′ increased from 6.22 to 6.44. The dissipation factor, tan δ, remained constant at 0.020. Similarly, as the crystallization time at 750° C increased from 0.5 hr to 6.0 hr, κ′ increased from 6.28 to 6.35. The deviations of the measured dielectric polarizabilities as determined from the Clausius-Mosotti equation from those calculated from the sum of oxide polarizabilities according to α D(mineral, glass) = σ α D(oxides) are +7.4% for α-spodumene, +1.2% for diopside, and +28.0, +19.6 and +15.9% for amorphous spodumene, anorthitie and diopside compositions, respectively. Positive deviations in α-spodumene and anorthite are consistent with lower than normal apparent cation bond valence sums and are believed to be evidence for loosely bonded “rattling” Li and Ca ions. Diopside, with Ca and Mg ions having normal bond valence sums, exhibits no abnormal deviation from additivity. Larger positive deviations in amorphous SiO2, LiAlSi2O6, CaAl2Si2O8 and CaMgSi2O6 are postulated to arise from a combination of loosely bonded cations and disordered O= ions where the oxygen dielectric polarizability increased from its normal value of 2.0 Å3 in well-behaved oxides to 2.2–3.0 Å3 in the amorphous phases.  相似文献   

5.
The dielectric constants and dielectric loss values of BeAl2O4 (chrysoberyl), MgAl2O4 (spinel), Be2SiO4 (phenacite), and Mg2SiO4 (forsterite) were measured at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: chrysoberyl, κ′ a =9.436, κ′ b =9.071, κ′ c =8.269; spinel, κ′ a =8.18; phenacite, κ′ a =6.28, κ′ c =6.06; and forsterite, κ′ a =6.867, κ′ b =7.392, κ′ c =6.739. The agreement between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to αD(M2M′X4) = 2αD(MX)+αD(M′X2) is ~ 1.0%.  相似文献   

6.
Crystals of the olivine minerals, tephroite (Mn2SiO4) and fayalite (Fe2SiO4) containing manganese(II) and iron (II and trace of III), respectively, were synthesized. Glasses were prepared from these crystalline materials by a splat-quench technique. Measurement of electron paramagnetic resonance (EPR) of all these powdered samples at room temperature show that the g-factors of Mn2+ in both glassy and crystalline environments (geff = 2.004) are the same, although the EPR linewidths (for glass, ΔHpp = 200 G; for crystals ΔHpp = 287 G) suggest less clustering of paramagnetic Mn2+ ions in the glass. Mn2+ probably occupies a distorted octahedral site in the tephroite crystal structure, although a four-fold coordination is suggested from other spectroscopic investigation on this glass. The EPR parameters of Fe3+ in synthetic fayalite glass (geff = 2.01 and 6.00; ΔHpp=150 and 1375 G, respectively, for the high and low field resonances) and powdered crystals (geff = 3.31 and ΔHpp = 900 G) indicated that Fe3+ ion in the crystals, is probably located in a distorted tetragonal site M2 and an axial environment has been proposed in the glassy system.  相似文献   

7.
Domain twinning of laihunite has been investigated based on diffracton phenomena, and its crystal structure has then been refined. Space group with respect to the domain isP21/c, and cell parametersa=5.813,b=4,812,c=10.211(A), β=90.87°. Atomic coordinate and bond length have been recalculated. Discussions are made of the Fe2+ distribution, lattice distortion, degree of order of laihunite and the relationship of this mineral with fayalite and ferrifayalite. The authors still hold that laih unite should be considered as a new silicate mineral with dominant Fe3+ and less amount of Fe2+.  相似文献   

8.
The maxima of the electron difference densities of Fe2+ atM(1) andM(2) positions of fayalite, Fe2SiO4, determined by x-ray diffraction are considered to correspond to atomic dipoles. Provided the selection rules of dipole radiation are satisfied and the energy of the incident radiation lies within the appropriate range, the interaction of incident radiation with these atomic dipoles should lead to three absorption bands of which two originate from Fe2+ atM(1), one from Fe2+ atM(2). The relative intensities of the three bands, dependent on the polarization direction, are estimated. The result ist in excellent agreement with the interpretation of olivine spectra given by Burns (1970).  相似文献   

9.
A member of the grunerite series (Fe6.685Mn0.142Ca0.110Mg0.096) (Si7.968Al0.016)O22(OH)2, has been transformed to clinoferrosilite, amorphous silica and water at 775° C and 500 bars Argon pressure. Single crystal photographs of an oriented intergrowth of the amphibole and pyroxene show that the clinoferrosilite retains the cristallographic a, b and c axes of the original grunerite in the I2/m orientation and has the cell dimensions: a=9.77, b=9.08, c=5.30 Å, =109.5°; space group P21/c. Mössbauer resonance spectroscopy confirmed the identity of the olinoferrosilite.A transformation mechanism requires a minimum of ionic movements in an acceptor region (7/8 of the total crystal), where pyroxene is formed by expulsion of protons and acceptance of Fe2+ ions; simultaneous destruction of donor regions provide the Fe2+ ions, the residue being silica and water. The formation of metastable clinoferrosilite rather than fayalite and quartz indicates the strong structural control imposed by the host grunerite structure on the nature of the transformation products.  相似文献   

10.
The iron-magnesium distribution coefficient, $$K'_D = (X_{\Sigma {\text{FeO}}} /X_{{\text{MgO}}} )^{{\text{olivine}}} (X_{{\text{MgO}}} /X_{\Sigma {\text{FeO}}} )^{{\text{liquid}}} ,$$ has frequently been used as a means of testing whether experimental and natural silicate liquids could have been in equilibrium with olivine of mantle composition. It is shown here that this K′ D decreases with increasing oxygen fugacity (xxx) for a hydrous partial melt in equilibrium with a natural spinel peridotite assemblage under pressure and temperature conditions corresponding to those of the upper mantle (from 0.52 at the xxx of the iron-wüstite buffer to 0.04 at the xxx of the magnetite-hematite buffer). K′ D also increases with increasing pressure, with decreasing temperature, and probably with increasing Mg/(Mg+∑ Fe) of the parental peridotite, suggesting that $$K_D = (X_{{\text{FeO}}} /X_{{\text{MgO}}} )^{{\text{olivine}}} (X_{{\text{MgO}}} /X_{{\text{FeO}}} )^{{\text{liquid}}}$$ also increases with increasing pressure and decreasing temperature. Thus, unless these four variables (P, T, xxx, silicate composition) are known for a natural magma, K′ D and probably K D are variables, and the Mg/(Mg+∑ Fe) of such a magma cannot be correlated to that of the parent. The K D determined at 1 atm pressure by Roeder and Emslie has frequently been used to test whether the Mg/(Mg+∑ Fe) ratios of experimentally formed liquids at high pressure in equilibrium with olivine of known Fo content represent the equilibrium Mg/(Mg+Fe2+) of this liquid, assuming that ∑Fe=Fe2+ and that K′ D does not vary with P, T, and composition of the system. Published data demonstrate that the oxygen fugacities of the experimental designs employed by different laboratories vary between those of the magnetite-hematite and magnetite-wüstite buffers (6 orders of magnitude), resulting in K′ D between 0.04 and 0.31 at 1050° C and 15 kbar, for example. Thus, published arguments as to whether the quenched liquids represent equilibrium compositions based on iron-magnesium partitioning are inadequate. The effects of P, T, xxx, and the composition of the starting material must also be considered.  相似文献   

11.
The high-pressure elastic behaviour of a synthetic zeolite mordenite, Na6Al6.02Si42.02O96·19H2O [a=18.131(2), b=20.507(2), c=7.5221(5) Å, space group Cmc21], has been investigated by means of in situ synchrotron X-ray powder diffraction up to 5.68 GPa. No phase transition has been observed within the pressure range investigated. Axial and volume bulk moduli have been calculated using a truncated second-order Birch–Murnaghan equation-of-state (II-BM-EoS). The refined elastic parameters are: V 0=2801(11) Å3, K T0= 41(2) GPa for the unit-cell volume; a 0=18.138(32) Å, K T0(a)=70(8) GPa for the a-axis; b 0=20.517(35) Å, K T0(b)=29(2) GPa for the b-axis and c 0=7.531(5) Å, K T0(c)=38(1) GPa for the c-axis [K T0(a): K T0(b): K T0(c)=2.41:1.00:1.31]. Axial and volume Eulerian finite strain versus “normalized stress” plots (fe–Fe plot) show an almost linear trend and the weighted linear regression through the data points yields the following intercept values: Fe(0)=39(4) GPa for V; Fe a (0)=65(18) GPa for a; Fe b (0)=28(3) GPa for b; Fe c (0)=38(2) GPa for c. The magnitudes of the principal Lagrangian unit-strain coefficients, between 0.47 GPa (the lowest HP-data point) and each measured P>0.47 GPa, were calculated. The unit-strain ellipsoid is oriented with ε1 || b, ε2 || c, ε3 || a and |ε1|> |ε2|> |ε3|. Between 0.47 and 5.68 GPa the relationship between the unit-strain coefficient is ε1: ε2: ε3=2.16:1.81:1.00. The reasons of the elastic anisotropy are discussed.An erratum to this article can be found at  相似文献   

12.
The diffusion, substitution mechanism and solubility limits of Zr and Hf in synthetic forsterite (Mg2SiO4) and San Carlos olivine (Mg0.9Fe0.1)2SiO4 have been investigated between 1,200 and 1,500 °C as a function of the chemical potentials of the components in the system MgO(FeO)–SiO2–ZrO2(HfO2). The effect of oxygen fugacity and crystallographic orientation were also investigated. The solubilities of Zr in forsterite are highest and diffusion fastest when the coexisting three-phase source assemblage includes ZrSiO4 (zircon) or HfSiO4 (hafnon), and lower and slower, respectively, when the source assemblage includes MgO (periclase). This indicates that Zr and Hf substitute on the octahedral sites in olivine, charge balanced by magnesium vacancies. Diffusion is anisotropic, with rates along the crystal axes increasing in the order a < b < c. The generalized diffusion relationship as a function of chemical activity (as \(a_{{{\text{SiO}}_{2} }}\)), orientation and temperature is: \(logD_{\text{Zr}} = \frac{1}{4}loga_{{{\text{SiO}}_{2} }} + logD_{0} - \left( {\frac{{368 \pm 17\;{\text{kJ}}\;{\text{mol}}^{ - 1} }}{{2.303\;{\text{RT}}}}} \right)\) where the values of log D 0 are ?3.8(±0.5), ?3.4(±0.5) and ?3.1(±0.5) along the a, b and c axes, respectively. Most experiments were conducted in air (fO2 = 10?0.68 bars), but one at fO2 = 10?11.2 bars at 1,400 °C shows no resolvable effect of oxygen fugacity on Zr diffusion. Hf is slightly more soluble in olivine than Zr, but diffuses slightly slower. Diffusivities of Zr in experiments in San Carlos olivine at 1,400 °C, fO2 = 10?6.6 bars are similar to those in forsterite at the same conditions, showing that the controls on diffusivities are adequately captured by the simple system (nominally iron-free) experiments. Diffusivities are in good agreement with those measured by Spandler and O’Neill (Contrib Miner Petrol 159:791–818, 2010) in San Carlos olivine using silicate melt as the source at 1,300 °C, and fall within the range of most measurements of Fe–Mg inter-diffusion in olivine at this temperature. Forsterite–melt partitioning experiments in the CaO–MgO–Al2O3–SiO2–ZrO2/HfO2 show that the interface concentrations from the diffusion experiments represent true equilibrium solubilities. Another test of internal consistency is that the ratios of the interface concentrations between experiments buffered by Mg2SiO4 + Mg2Si2O6 + ZrSiO4 or Mg2SiO4 + ZrSiO4 + ZrO2 (high silica activity) to those buffered by Mg2SiO4 + MgO + ZrO2 (low silica activity) agree well with the ratios calculated from thermodynamic data. This study highlights the importance of buffering chemical potentials in diffusion experiments to provide constraints on the interface diffusant concentrations and hence validate the assumption of interface equilibrium.  相似文献   

13.
Kinetics of diffusion-controlled growth of fayalite   总被引：1，自引：0，他引：1  
The rate of growth of fayalite (Fe2SiO4) has been measured at one atmosphere total pressure, temperatures from 1000° to 1120° C, and oxygen fugacities controlled by CO/CO2 gas-mixing from 10-9.9 to 10-13.0atm, chosen to span the fayalite stability field. The fine-grained polycrystalline fayalite layer was formed by reacting the oxides FeO or Fe3O4 with a thin slice of single-crystal quartz. The rate of growth of the fayalite increases with increasing temperature and decreasing oxygen fugacity, and is consistent with a parabolic rate law, indicating that the growth rate is controlled by diffusion through the fayalite. Microstructural observations and platinum marker experiments suggest that the reaction phase is formed at the quartz-fayalite interface, and is therefore controlled by the diffusion of iron and oxygen. The parabolic rate constant was analyzed in terms of the oxide activity gradient to yield mean chemical diffusivities for the rate-limiting ionic species, assuming bulk transport through the fayalite layer. Given that iron diffusion in olivine polycrystals occurs either by lattice diffusion, which shows a positive dependence on oxygen activity, or by grain boundary diffusion, which would result in growth rates significantly faster than we observe, we conclude that the diffusivities derived in this study represent oxygen diffusion. However, since oxygen lattice diffusion in fayalite has been established to be much slower than our measurements, it is likely that the transport path for oxygen is along the grain boundaries. Thus, the mean grain boundary diffusivity of oxygen in fayalite $\bar D$ O gb (m2 s-1), using the measured grain size of 0.25 μm, is then given by $$\bar D_O^{gb} {\mathbf{ }}\delta = 1.28 \times 10^{ - 3} f_{O_2 }^{ - 0.17} {\mathbf{ }}e^{ - 540/RT} $$ , where δ is the grain boundary width (in m), and the activation energy is in kJ/mol. Assuming δ=10-9 m (Ricoult and Kohlstedt 1983), the oxygen grain boundary diffusivities are about a factor of 30 × slower than those reported by Watson (1986) for Fo90 olivine.  相似文献   

14.
A new superstructure was found in bafertisite [(Ba0.98Na0.02)1.00(Fe1.71Mn0.26Mg0.01)1.98 TiO[(Si1.82Ti0.04Al0.03Cr0.01)1.90O7](OH1.40F0.53Cl0.03)1.96] from Donghai County, Jiangsu Province, China. The occurrence of the superstructure reflections were observed by single crystal diffraction using a SMAR APEX CCD. The a*, b*and c* axis directions revealed extra weak reflection spots of the superstructure. The apparent 2a, 2b and 2c superstructure is monoclinic with unit cell a＝10.6502(15)?, b＝13.7233(19)?, c＝21.6897(3)?, α＝90o, β＝94.698(3)o, γ＝90o,space group Cm,Z=16. If c* extra weak reflections are ignored, the secondary supercell gave a cell a＝10.6548(15)?, b＝13.7284(19)?, c＝11.6900(17)?, α＝90o, β＝112.322(28)o, γ＝90o,space group Cm,Z=8. The basic subcell was obtained by ignoring all extra weak reflection spots and gave: a＝5.3249(17)?, b＝6.8669(22)?, c＝10.8709(36)?, α＝90o, β＝94.740(62)o, γ＝90o,space P21/m,Z=2. The superstructure has been refined to R = 0.063 for 7805 [R(int) = 0.0266] unique reflections I>2δ(I). The structure consists of an octahedra (O) sheet sandwiched between two heteropolyhedral (H) sheets. These sheets consist of Ti–octahedra and twin tetrahedral disilicate groups [Si2O7]. The O sheet comprises (Fe,Mg)O4 octahedra. The large Ba cation is located in the interlayer area. The refined structure shows Fe, Mg are partly ordered. The shifting of the TiO6 octahedron and SiO4 tetrahedron sites in the sheet may be a consequence of the superstructure.  相似文献   

15.
The enthalpies of solution of synthetic Mg2SiO4-Fe2SiO4 olivine solid solutions have been measured in Pb2B2O5 melt at 970 K. The heat of solution of forsterite was found to be 15.62 ± 0.3 kcal mol?1 and that of fayalite 9.39 ± 0.14 kcal mol?1. Solid solutions between these end-members exhibit small positive deviations from mixing ideality, asymmetric towards the Fe end-member. In terms of the sub-regular solution model, excess enthalpies of intermediate olivine are adequately represented by the equation Hxs = 2(1000 + 1000XFe) XFeXMgThe enthalpies of solution at 970 K are consistent with high temperature phase equilibrium measurements of activity-composition relationships in the olivine series. Excess entropy terms are not needed to relate the phase equilibrium data to the calorimetric data presented here.The enthalpy of solution of FeSiO3 ferrosilite at 970 K was found to be 4.36 ± 0.10 kcal mol?1. This value, when taken together with calorimetric measurements on fayalite and quartz, is consistent with phase equilibrium investigations of the reaction: 2FeSiO3 = Fe2SiO4 + SiO2 Ferrosilite Fayalite QuartzThese provide a check on the internal consistency of the calorimetric data presented here.  相似文献   

16.
We experimentally investigated the phase relations of a peralkaline phonolitic dyke rock associated with the Ilímaussaq plutonic complex (South Greenland). The extremely evolved and iron-rich composition (magnesium number = 2, alkalinity index = 1.44, FeO* = 12 wt%) may represent the parental magma of the Ilímaussaq complex. This dyke rock is therefore perfectly suited for performing phase-equilibrium experiments, since in contrast to the plutonic rocks of the complex, no major cumulate formation processes complicate defining a reasonable starting composition. Experiments were carried out in hydrothermal rapid-quench cold-seal pressure vessels at P = 100 MPa and T = 950–750 °C. H2O contents ranging from anhydrous to H2O saturated (~5 wt% H2O) and varying fO2 (~ΔlogFMQ ?3 to +1; where FMQ represents the fayalite–magnetite–quartz oxygen buffer) were applied. Reduced and dry conditions lead to substantial crystallization of alkali feldspar, nepheline, hedenbergite-rich clinopyroxene, fayalite-rich olivine and minor amounts of ulvøspinel-rich magnetite, which represent the phenocryst assemblage of the natural dyke rock. Oxidized and H2O-rich conditions, however, suppress the crystallization of olivine in favor of magnetite and clinopyroxene with less or no alkali feldspar and nepheline formation. Accordingly, combined low fO2 and aH2O force the evolution of the residual melt toward decreasing SiO2, increasing FeO* and alkalinity index (up to 3.55). On the contrary, high fO2 and aH2O produce residual melts with relatively low FeO*, high SiO2 and a relatively constant alkalinity index. We show that variations of aH2O and fO2 lead to contrasting trends regarding the liquid lines of descent of iron-rich silica-undersaturated peralkaline compositions. Moreover, the increase in FeO* and alkalinity index (reduced and dry conditions) in the residual melt is an important prerequisite to stabilize late-magmatic minerals of the dyke rock, for example, aenigmatite (Na2Fe5TiSi6O20), coexisting with the most evolved melts at 750 °C. Contrary to what might be expected, experiments with high aH2O and interlinked high fO2 exhibit higher liquidus T’s compared with experiments performed at low aH2O and fO2 for experiments where magnetite is liquidus phase. This is because ulvøspinel-poor magnetite crystallizes at higher fO2 and has a higher melting point than ulvøspinel-rich magnetite, which is favored at lower fO2.  相似文献   

17.
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   

18.
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   

19.
Lithian ferrian enstatite with Li2O = 1.39 wt% and Fe2O3 7.54 wt% was synthesised in the (MgO–Li2O–FeO–SiO2–H2O) system at P = 0.3 GPa, T = 1,000°C, fO2 = +2 Pbca, and a = 18.2113(7), b = 8.8172(3), c = 5.2050(2) Å, V = 835.79(9) Å3. The composition of the orthopyroxene was determined combining EMP, LA-ICP-MS and single-crystal XRD analysis, yielding the unit formula M2(Mg0.59Fe 0.21 2+ Li0.20) M1(Mg0.74Fe 0.20 3+ Fe 0.06 2+ ) Si2O6. Structure refinements done on crystals obtained from synthesis runs with variable Mg-content show that the orthopyroxene is virtually constant in composition and hence in structure, whereas coexisting clinopyroxenes occurring both as individual grains or thin rims around the orthopyroxene crystals have variable amounts of Li, Fe3+ and Mg contents. Structure refinement shows that Li is ordered at the M2 site and Fe3+ is ordered at the M1 site of the orthopyroxene, whereas Mg (and Fe2+) distributes over both octahedral sites. The main geometrical variations observed for Li-rich samples are actually due to the presence of Fe3+, which affects significantly the geometry of the M1 site; changes in the geometry of the M2 site due to the lower coordination of Li are likely to affect both the degree and the kinetics of the non-convergent Fe2+-Mg ordering process in octahedral sites.  相似文献   

20.
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   

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