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1.
We present structural information obtained on spinel and alumina at high temperature (298-2400 K) using in-situ XANES at the Mg and Al K-edges. For spinel, [4](Alx,Mg1−x)[6](Al2−x,Mgx)O4, with increasing temperature, a substitution of Mg by Al and Al by Mg in their respective sites is observed. This substitution corresponds to an inversion of the Mg and Al sites. There is a significant change in the Al K-edge spectra between crystal and liquid, which can be attributed to a change of the [6]Al normally observed in corundum at room temperature, to a mixture of [6]Al-[4]Al in the liquid state. This conclusion is in good agreement with previous 27Al NMR experiments. Furthermore, both experiments at the Al and Mg K-edges are in good agreement with XANES calculation made using FDMNES code.  相似文献   

2.
The rate of spinel (MgAl2O4) growth at the interface between MgO and Al2O3 was investigated systematically at temperatures of 1200° to ∼2000°C and pressures between 1.0 and 4.0 GPa with a solid-media, piston-cylinder apparatus. As reported in previous 1-atm studies, the thickness (ΔX) of the spinel layer increases linearly with the square root of time for experiments differing only in duration, irrespective of pressure-temperature (P-T) conditions. The reaction rate constant (k = ΔX2/2t) is log-linear in 1/T and also in pressure. The apparent activation energy of 410 kJ/mol is independent of pressure; the apparent activation volume increases systematically with increasing temperature. Electron microprobe traverses across the spinel layer reveal a significant Al excess and charge-compensating Mg deficit near the spinel/corundum interface. This nonstoichiometry is promoted by high temperatures (>1500°C), suppressed by high pressures and varies linearly across the spinel to a near-stoichiometric composition at the interface with periclase. The Al and Mg composition gradients can be used to extract interdiffusion coefficients for Al ↔ Mg exchange through the spinel, which are described by D?=2.5×10−6 exp(−28200/T) m2sThese diffusivities differ substantially from the reaction rate constant k, reflecting the fact that k is a combination of the diffusivity and the reaction potential as indicated by the difference in spinel composition across the spinel layer (i.e., coexisting with corundum vs. coexisting with periclase). A simple model can be used to separate the two effects and show that the reaction potential (i.e., the MgO-Al2O3 phase diagram) is sensitive to changes in both temperature and pressure, whereas the governing diffusivity depends only on temperature.  相似文献   

3.
Solubility and solution mechanisms of H2O in depolymerized melts in the system Na2O-Al2O3-SiO2 were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na2Si4O9-Na2(NaAl)4O9] with Al/(Al+Si) = 0.00-0.25. The H2O solubility was fitted to the expression, XH2O=0.20+0.0020fH2O-0.7XAl+0.9(XAl)2, where XH2O is the mole fraction of H2O (calculated with O = 1), fH2O the fugacity of H2O, and XAl = Al/(Al+Si). Partial molar volume of H2O in the melts, , calculated from the H2O-solulbility data assuming ideal mixing of melt-H2O solutions, is 12.5 cm3/mol for Al-free melts and decreases linearly to 8.9 cm3/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H2O, , increases with Al/(Al+Si).Solution mechanisms of H2O were obtained by combining Raman and 29Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H2O content. The rate of NBO/T-change with H2O is negatively correlated with H2O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q4-species to form Q2 species. Steric hindrance appears to restrict bonding of H+ with nonbridging oxygen in Q3 species. The presence of Al3+ does not affect the water solution mechanisms significantly.  相似文献   

4.
We have determined the P-V equation of state of Al-rich H-bearing SiO2 stishovite by X-ray powder diffraction at pressures up to 58 GPa using synchrotron radiation. The sample contained 1.8 wt% Al2O3 and up to 500 ppm H2O, and had a composition that would coexist with Mg-silicate perovskite in a subducted slab. By fitting a third-order Birch-Murnaghan equation of state to our compression data, we obtained a bulk modulus K T0=298(7) GPa with K′=4.3(5). With K′ fixed to a value of 4, the bulk modulus K T0=304(3) GPa. Our results indicate that Al3+ and H+ have a small effect on the elastic properties of stishovite. Compared with data obtained up to 43.8 GPa, peak intensities changed and we observed a decreased quality of fit to a tetragonal unit cell at pressures of 49 GPa and higher. These changes may be an indication that the rutile↔CaCl2 transition occurs between these pressures. After laser annealing of the sample at 58.3(10) GPa and subsequent decompression to room conditions, the cell volume is the same as before compression, giving strong evidence that the composition of the recovered sample is also unchanged. This suggests that Al and H are retained in the sample under extreme P-T conditions and that stishovite can be an agent for transporting water to the deepest lower mantle.  相似文献   

5.
Diffusion coefficients of Cr and Al in chromite spinel have been determined at pressures ranging from 3 to 7 GPa and temperatures ranging from 1,400 to 1,700°C by using the diffusion couple of natural single crystals of MgAl2O4 spinel and chromite. The interdiffusion coefficient of Cr–Al as a function of Cr# (=Cr/(Cr + Al)) was determined as D Cr–Al = D 0 exp {−(Q′ + PV*)/RT}, where D 0 = exp{(10.3 ± 0.08) × Cr#0.54±0.02} + (1170 ± 31.2) cm2/s, Q′ = 520 ± 81 kJ/mol at 3 GPa, and V* = 1.36 ± 0.25 cm3/mol at 1,600°C, which is applicable up to Cr# = 0.8. The estimation of the self-diffusion coefficients of Cr and Al from Cr–Al interdiffusion shows that the diffusivity of Cr is more than one order of magnitude smaller than that of Al. These results are in agreement with patterns of multipolar Cr–Al zoning observed in natural chromite spinel samples deformed by diffusion creep.  相似文献   

6.
We performed density measurements on a synthetic equivalent of lunar Apollo 17 74,220 “orange glass”, containing 9.1 wt% TiO2, at superliquidus conditions in the pressure range 0.5-8.5 GPa and temperature range 1723-2223 K using the sink/float technique. In the lunar pressure range, two experiments containing pure forsterite (Fo100) spheres at 1.0 GPa and 1727 K, and at 1.3 GPa-1739 K, showed neutral buoyancies, indicating that the density of molten orange glass was equal to the density of Fo100 at these conditions (3.09 ± 0.02 g cm−3). A third tight sink/float bracket using Fo90 spheres corresponds to a melt density of 3.25 ± 0.02 g cm−3 at ∼2.8 GPa and ∼1838 K.Our data predict a density crossover for the molten orange glass composition with equilibrium orthopyroxene at ∼2.8 GPa, equivalent to a depth of ∼600 km in the lunar mantle, and a density of ∼3.25 g cm−3. This crossover depth is close to the orange glass multiple saturation point, representing its minimum formation depth, at the appropriate oxygen fugacity (2.8-2.9 GPa). A density crossover with equilibrium olivine is predicted to fall outside the lunar pressure range (>4.7 GPa), indicating that molten orange glass is always less dense than its equilibrium olivines in the Moon. Our data therefore suggest that that lunar liquids with orange glass composition are buoyant with respect to their source region at P < ∼2.8 GPa, enabling their initial rise to the surface without the need for additional external driving forces.Fitting the density data to a Birch-Murnaghan equation of state at 2173 K leads to an array of acceptable solutions ranging between 16.1 and 20.3 GPa for the isothermal bulk modulus K2173 and 3.6-8 for its pressure derivative K′, with best-fit values K2173 = 18.8 GPa and K′ = 4.4 when assuming a model 1 bar density value of 2.86 g cm−3. When assuming a slightly lower 1 bar density value of 2.84 g cm−3 we find a range for K2173 of 14.4-18.0 and K′ 3.7-8.7, with best-fit values of 17.2 GPa and 4.5, respectively.  相似文献   

7.
The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K1.38Na0.05)(Al2.87Mg0.46Fe3+0.39Fe2+0.28Ti0.07)[Si7.02Al0.98]O20(OH)4 was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H2SO4) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K+ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na+ from the solution and K+ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower RAl (dissolution rate calculated from steady state Al release) than RSi (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.  相似文献   

8.
The heat capacity and vibrational entropy of a calcium aluminate and three peraluminous calcium aluminosilicate glasses have been determined from 2 to 300 K by heat-pulse relaxation calorimetry. Together with previous adiabatic data for six other glasses in the system CaO-Al2O3-SiO2, these results have been used to determine partial molar heat capacities and entropies for five species namely, SiO2, CaO and three different sorts of Al2O3 in which Al is 4-, 5- and 6-fold coordinated by oxygen. Given the determining role of oxygen coordination on low-temperature heat capacity, the composition independent entropies found for SiO2 and CaO indicate that short-range order around Si and Ca is not sensitive to aluminum speciation up to the highest fraction of 25% observed for VAl by NMR spectroscopy. Because of the higher room-temperature vibrational entropy of IVAl2O3 (72.8 J/mol K) compared to VAl2O3 (48.5 J/mol K), temperature-induced changes from IVAl to VAl give rise to a small negative contribution of the order of 1 J/mol K to the partial molar configurational heat capacity of Al2O3 in melts. Near 0 K, pure SiO2 glass distinguishes itself by the importance of the calorimetric boson peak. On a g atom basis, the maximum of this peak varies with the composition of calcium aluminosilicate glasses by a factor of about 2. It does not show smooth variations, however, either as a function of SiO2 content, at constant CaO/Al2O3 ratio, or as a function of Al2O3 content, at constant SiO2 content.  相似文献   

9.
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   

10.
The elastic behaviour and the high-pressure structural evolution of a natural topaz, Al2.00Si1.05O4.00(OH0.26F1.75), have been investigated by means of in situ single-crystal X-ray diffraction up to 10.55(5) GPa. No phase transition has been observed within the pressure range investigated. Unit-cell volume data were fitted with a third-order Birch-Murnaghan Equation of State (III-BM-EoS). The III-BM-EoS parameters, simultaneously refined using the data weighted by the uncertainties in P and V, are: V 0=345.57(7) Å3, K T0=164(2) GPa and K′=2.9(4). The axial-EoS parameters are: a 0=4.6634(3) Å, K T0(a)=152(2) GPa, K′(a)=2.8(4) for the a-axis; b 0=8.8349(5) Å, K T0(b)=224(3) GPa, K′(b)=2.6(6) for the b-axis; c 0=8.3875(7) Å, K T0(c)=137(2) GPa, K′(c)=2.9(4) for the c-axis. The magnitude and the orientation of the principal Lagrangian unit-strain ellipsoid were determined. At P−P 0=10.55 GPa, the ratios ε1:ε2:ε3 are 1.00:1.42:1.56 (with ε1||b, ε2||a, ε3||c and |ε3| > |ε2| > |ε1|). Four structural refinements, performed at 0.0001, 3.14(5), 5.79(5) and 8.39(5) GPa describe the structural evolution in terms of polyhedral distortions.  相似文献   

11.
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12.
The high-pressure (HP) behaviour of a natural orthorhombic and tetragonal edingtonite from Ice River, Canada, has been investigated using in situ single-crystal X-ray diffraction. The two isothermal equations of state up to 6.74(5) GPa were determined. V0, KT0 and K refined with a third-order Birch–Murnaghan equation of state (BM-EoS) are: V0 = 598.70(7) Å3, KT0 = 59(1) GPa and K=3.9(4) for orthorhombic edingtonite and V0 = 600.9(2) Å3, KT0 = 59(1) GPa and K=4.2(5) for tetragonal edingtonite. The experiments were conducted with nominally hydrous pressure penetrating transmitting medium. No overhydration effect was observed within the pressure range investigated. At high-pressures the main deformation mechanism is represented by cooperative rotation of the secondary building unit (SBU).Si/Al distribution slightly influences the elastic behaviour of the tetrahedral framework: the SBU bulk moduli are 125(8) GPa and 111(4) GPa for orthorhombic and tetragonal edingtonite, respectively. Extra-framework contents of both zeolites show an interesting behaviour under HP conditions: the split Ba2 site at P >2.85 GPa is completely empty; only the position Ba1 is occupied. Electronic Supplementary Material. Supplementary material to this paper (Observed and calculated structure factors) is available in electronic form at Electronic Supplementary Material Supplementary material is available in the online version of this article at  相似文献   

13.
The heat capacities of the international reference clay mineral chlorite CCa-2 from Flagstaff Hill, California, were measured by low temperature adiabatic calorimetry and differential scanning calorimetry, from 5 to 520 K (at 1 bar). The studied chlorite is a Fe-bearing trioctahedral chlorite with an intermediary composition between ideal clinochlore (Si3Al)(Mg5Al)O10(OH)8 and chamosite (Si3Al)(Fe5Al)O10(OH)8. Only few TiO2 impurities were detected in the natural chlorite sample CCa-2. Its structural formula, obtained after subtracting the remaining TiO2 impurities, is (Si2.633Al1.367)(Al1.116Mg2.952Mn0.012Ca0.011)O10(OH)8. From the heat capacity results, the entropy, standard entropy of formation and heat content of the chlorite were deduced. At 298.15 K, the heat capacity of the chlorite is 547.02 (±0.27) J mol−1 K−1 and the molar entropy is 469.4 (±2.9) J mol−1 K−1. The standard molar entropy of formation of the clay mineral from the elements is −2169.4 (±4.0) J mol−1 K−1.  相似文献   

14.
Wadeite-type K2Si4O9 was synthesized with a cubic press at 5.4 GPa and 900 °C for 3 h. Its unit-cell parameters were measured by in situ high-T powder X-ray diffraction up to 600 °C at ambient P. The T–V data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (αT = a 0 + a 1 T), yielding a 0 = 2.47(21) × 10?5 K?1 and a 1 = 1.45(36) × 10?8 K?2. Compression experiments at ambient T were conducted up to 10.40 GPa with a diamond-anvil cell combined with synchrotron X-ray radiation. A second-order Birch–Murnaghan equation of state was used to fit the P–V data, yielding K T = 97(3) GPa and V 0 = 360.55(9) Å3. These newly determined thermal expansion data and compression data were used to thermodynamically calculate the P–T curves of the following reactions: 2 sanidine (KAlSi3O8) = wadeite (K2Si4O9) + kyanite (Al2SiO5) + coesite (SiO2) and wadeite (K2Si4O9) + kyanite (Al2SiO5) + coesite/stishovite (SiO2) = 2 hollandite (KAlSi3O8). The calculated phase boundaries are generally consistent with previous experimental determinations.  相似文献   

15.
The behavior of a natural topaz, Al2.00Si1.05O4.00(OH0.26F1.75), has been investigated by means of in situ single-crystal synchrotron X-ray diffraction up to 45 GPa. No phase transition or change in the compressional regime has been observed within the pressure-range investigated. The compressional behavior was described with a third-order Birch–Murnaghan equation of state (III-BM-EoS). The III-BM-EoS parameters, simultaneously refined using the data weighted by the uncertainties in P and V, are as follows: K V = 158(4) GPa and K V ′ = 3.3(3). The confidence ellipse at 68.3 % (Δχ2 = 2.30, 1σ) was calculated starting from the variance–covariance matrix of K V and K′ obtained from the III-BM-EoS least-square procedure. The ellipse is elongated with a negative slope, indicating a negative correlation of the parameters K V and K V ′, with K V = 158 ± 6 GPa and K V ′ = 3.3 ± 4. A linearized III-BM-EoS was used to obtain the axial-EoS parameters (at room-P), yielding: K(a) = 146(5) GPa [β a = 1/(3K(a)) = 0.00228(6) GPa?1] and K′(a) = 4.6(3) for the a-axis; K(b) = 220(4) GPa [β b = 0.00152(4) GPa?1] and K′(b) = 2.6(3) for the b-axis; K(c) = 132(4) GPa [β c = 0.00252(7) GPa?1] and K′(c) = 3.3(3) for the c-axis. The elastic anisotropy of topaz at room-P can be expressed as: K(a):K(b):K(c) = 1.10:1.67:1.00 (β a:β b:β c = 1.50:1.00:1.66). A series of structure refinements have been performed based on the intensity data collected at high pressure, showing that the P-induced structure evolution at the atomic scale is mainly represented by polyhedral compression along with inter-polyhedral tilting. A comparative analysis of the elastic behavior and P/T-stability of topaz polymorphs and “phase egg” (i.e., AlSiO3OH) is carried out.  相似文献   

16.
The thermo-elastic behavior of a natural epidote [Ca1.925 Fe0.745Al2.265Ti0.004Si3.037O12(OH)] has been investigated up to 1,200 K (at 0.0001 GPa) and 10 GPa (at 298 K) by means of in situ synchrotron powder diffraction. No phase transition has been observed within the temperature and pressure range investigated. P–V data fitted with a third-order Birch–Murnaghan equation of state (BM-EoS) give V 0 = 458.8(1)Å3, K T0 = 111(3) GPa, and K′ = 7.6(7). The confidence ellipse from the variance–covariance matrix of K T0 and K′ from the least-square procedure is strongly elongated with negative slope. The evolution of the “Eulerian finite strain” vs “normalized stress” yields Fe(0) = 114(1) GPa as intercept values, and the slope of the regression line gives K′ = 7.0(4). The evolution of the lattice parameters with pressure is slightly anisotropic. The elastic parameters calculated with a linearized BM-EoS are: a 0 = 8.8877(7) Å, K T0(a) = 117(2) GPa, and K′(a) = 3.7(4) for the a-axis; b 0 = 5.6271(7) Å, K T0(b) = 126(3) GPa, and K′(b) = 12(1) for the b-axis; and c 0 = 10.1527(7) Å, K T0(c) = 90(1) GPa, and K’(c) = 8.1(4) for the c-axis [K T0(a):K T0(b):K T0(c) = 1.30:1.40:1]. The β angle decreases with pressure, βP(°) = βP0 −0.0286(9)P +0.00134(9)P 2 (P in GPa). The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α0 + α1 T −1/2. The refined parameters for epidote are: α0 = 5.1(2) × 10−5 K−1 and α1 = −5.1(6) × 10−4 K1/2 for the unit-cell volume, α0(a) = 1.21(7) × 10−5 K−1 and α1(a) = −1.2(2) × 10−4 K1/2 for the a-axis, α0(b) = 1.88(7) × 10−5 K−1 and α1(b) = −1.7(2) × 10−4 K1/2 for the b-axis, and α0(c) = 2.14(9) × 10−5 K−1 and α1(c) = −2.0(2) × 10−4 K1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α0(a): α0(b): α0(c) = 1 : 1.55 : 1.77. The β angle increases continuously with T, with βT(°) = βT0 + 2.5(1) × 10−4 T + 1.3(7) × 10−8 T 2. A comparison between the thermo-elastic parameters of epidote and clinozoisite is carried out.  相似文献   

17.
The solubility and incorporation mechanisms of water in synthetic and natural MgAl2O4 spinel have been investigated in a series of high-pressure/temperature annealing experiments. In contrast to most other nominally anhydrous minerals, natural spinel appears to be completely anhydrous. On the other hand, non-stoichiometric Al-rich synthetic (defect) spinel can accommodate several hundred ppm water in the form of structurally-incorporated hydrogen. Infrared (IR) spectra of hydrated defect spinel contain one main O-H stretching band at 3343-3352 cm−1 and a doublet consisting of two distinct O-H bands at 3505-3517 cm−1 and 3557-3566 cm−1. IR spectra and structural refinements based on single-crystal X-ray data are consistent with hydrogen incorporation in defect spinel onto both octahedral and tetrahedral O-O edges. Fine structure of O-H bands in IR spectra can be explained by partial coupling of interstitial hydrogen with cation vacancies, or by the effects of Mg-Al disorder on the tetrahedral site. The concentration of cation vacancies in defect spinel is a major control on hydrogen affinity. The commercial availability of large single crystals of defect spinel coupled with high water solubility and similarities in water incorporation mechanisms between hydrous defect spinel and hydrous ringwoodite (Mg2SiO4) suggests that synthetic defect spinel may be a useful low-pressure analogue material for investigating the causes and consequences of water incorporation in the lower part of Earth’s mantle transition zone.  相似文献   

18.
The thermoelastic parameters of synthetic Mn3Al2Si3O12 spessartine garnet were examined in situ at high pressure up to 13 GPa and high temperature up to 1,100 K, by synchrotron radiation energy dispersive X-ray diffraction within a DIA-type multi-anvil press apparatus. The analysis of room temperature data yielded K 0 = 172 ± 4 GPa and K 0 ′  = 5.0 ± 0.9 when V 0,300 is fixed to 1,564.96 Å3. Fitting of P–V–T data by means of the high-temperature third-order Birch–Murnaghan EoS gives the thermoelastic parameters: K 0 = 171 ± 4 GPa, K 0 ′  = 5.3 ± 0.8, (?K 0,T /?T) P  = ?0.049 ± 0.007 GPa K?1, a 0 = 1.59 ± 0.33 × 10?5 K?1 and b 0 = 2.91 ± 0.69 × 10?8 K?2 (e.g., α 0,300 = 2.46 ± 0.54 × 10?5 K?1). Comparison with thermoelastic properties of other garnet end-members indicated that the compression mechanism of spessartine might be the same as almandine and pyrope but differs from that of grossular. On the other hand, at high temperature, spessartine softens substantially faster than pyrope and grossular. Such softening, which is also reported for almandine, emphasize the importance of the cation in the dodecahedral site on the thermoelastic properties of aluminosilicate garnet.  相似文献   

19.
The thermo-elastic behaviour of Be2BO3(OH)0.96F0.04 (i.e. natural hambergite, Z = 8, a = 9.7564(1), b = 12.1980(2), c = 4.4300(1) Å, V = 527.21(1) Å3, space group Pbca) has been investigated up to 7 GPa (at 298 K) and up to 1,100 K (at 0.0001 GPa) by means of in situ single-crystal X-ray diffraction and synchrotron powder diffraction, respectively. No phase transition or anomalous elastic behaviour has been observed within the pressure range investigated. P?V data fitted to a third-order Birch–Murnaghan equation of state give: V 0 = 528.89(4) Å3, K T0 = 67.0(4) GPa and K′ = 5.4(1). The evolution of the lattice parameters with pressure is significantly anisotropic, being: K T0(a):K T0(b):K T0(c) = 1:1.13:3.67. The high-temperature experiment shows evidence of structure breakdown at T > 973 K, with a significant increase in the full-width-at-half-maximum of all the Bragg peaks and an anomalous increase in the background of the diffraction pattern. The diffraction pattern was indexable up to 1,098 K. No new crystalline phase was observed up to 1,270 K. The diffraction data collected at room-T after the high-temperature experiment showed that the crystallinity was irreversibly compromised. The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α 0 + α 1 T ?1/2. The refined parameters for Be2BO3(OH)0.96F0.04 are: α 0 = 7.1(1) × 10?5 K?1 and α 1 = ?8.9(2) × 10?4 K ?1/2 for the unit-cell volume, α 0(a) = 1.52(9) × 10?5 K?1 and α 1(a) = ?1.4(2) × 10?4 K ?1/2 for the a-axis, α 0(b) = 4.4(1) × 10?5 K?1 and α 1(b) = ?5.9(3) × 10?4 K ?1/2 for the b-axis, α 0(c) = 1.07(8) × 10?5 K?1 and α 1(c) = ?1.5(2) × 10?4 K ?1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α 0(a):α 0(b):α 0(c) = 1.42:4.11:1. The main deformation mechanisms in response to the applied temperature, based on Rietveld structure refinement, are discussed.  相似文献   

20.
The thermoelastic behavior of a natural clintonite-1M [with composition: Ca1.01(Mg2.29Al0.59Fe0.12)Σ3.00(Si1.20Al2.80)Σ4.00O10(OH)2] has been investigated up to 10 GPa (at room temperature) and up to 960°C (at room pressure) by means of in situ synchrotron single-crystal and powder diffraction, respectively. No evidence of phase transition has been observed within the pressure and temperature range investigated. P–V data fitted with an isothermal third-order Birch–Murnaghan equation of state (BM-EoS) give V 0 = 457.1(2) ?3, K T0 = 76(3)GPa, and K′ = 10.6(15). The evolution of the “Eulerian finite strain” versus “normalized stress” shows a linear positive trend. The linear regression yields Fe(0) = 76(3) GPa as intercept value, and the slope of the regression line leads to a K′ value of 10.6(8). The evolution of the lattice parameters with pressure is significantly anisotropic [β(a) = 1/3K T0(a) = 0.0023(1) GPa−1; β(b) = 1/3K T0(b) = 0.0018(1) GPa−1; β(c) = 1/K T0(c) = 0.0072(3) GPa−1]. The β-angle increases in response to the applied P, with: βP = β0 + 0.033(4)P (P in GPa). The structure refinements of clintonite up to 10.1 GPa show that, under hydrostatic pressure, the structure rearranges by compressing mainly isotropically the inter-layer Ca-polyhedron. The bulk modulus of the Ca-polyhedron, described using a second-order BM-EoS, is K T0(Ca-polyhedron) = 41(2) GPa. The compression of the bond distances between calcium and the basal oxygens of the tetrahedral sheet leads, in turn, to an increase in the ditrigonal distortion of the tetrahedral ring, with ∂α/∂P ≈ 0.1°/GPa within the P-range investigated. The Mg-rich octahedra appear to compress in response to the applied pressure, whereas the tetrahedron appears to behave as a rigid unit. The evolution of axial and volume thermal expansion coefficient α with temperature was described by the polynomial α(T) = α0 + α1 T −1/2. The refined parameters for clintonite are as follows: α0 = 2.78(4) 10−5°C−1 and α1 = −4.4(6) 10−5°C1/2 for the unit-cell volume; α0(a) = 1.01(2) 10−5°C−1 and α1(a) = −1.8(3) 10−5°C1/2 for the a-axis; α0(b) = 1.07(1) 10−5°C−1 and α1(b) = −2.3(2) 10−5°C1/2 for the b-axis; and α0(c) = 0.64(2) 10−5°C−1 and α1(c) = −7.3(30) 10−6°C1/2for the c-axis. The β-angle appears to be almost constant within the given T-range. No structure collapsing in response to the T-induced dehydroxylation was found up to 960°C. The HP- and HT-data of this study show that in clintonite, the most and the less expandable directions do not correspond to the most and the less compressible directions, respectively. A comparison between the thermoelastic parameters of clintonite and those of true micas was carried out.  相似文献   

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