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1.
High-pressure single-crystal X-ray diffraction measurements of lattice parameters of the compound Li2VOSiO4, which crystallises with a natisite-type structure, has been carried out to a pressure of 8.54(5) GPa at room temperature. Unit-cell volume data were fitted with a second-order Birch-Murnaghan EoS (BM-EoS), simultaneously refining V 0 and K 0 using the data weighted by the uncertainties in V. The bulk modulus is K 0 = 99(1) GPa, with K′ fixed to 4. Refinements of third order equations-of-state yielded values of K′ that did not differ significantly from 4. The compressibility of the unit-cell is strongly anisotropic with the c axis (K 0(c) = 49.7 ± 0.5 GPa) approximately four times more compressible than the a axis (K 0(a) = 195 ± 3 GPa).  相似文献   

2.
The pseudo-binary system CaMgSi2O6-KAlSi2O6, modeling the potassium-bearing clinopyroxene (KCpx) solid solution, has been studied at 7 GPa and 1,100–1,650 °C. The KCpx is a liquidus phase of the system up to 60 mol% of KAlSi2O6. At higher content of KAlSi2O6 in the system, grossular-rich garnet becomes a liquidus phase. Above 75 mol% of KAlSi2O6 in the system, KCpx is unstable at the solidus as well, and garnet coexists with kalsilite, Si-wadeite and kyanite. No coexistence of KCpx with kyanite was observed. Above the solidus, KAlSi2O6 content of the KCpx coexisting with melt increases with decreasing temperature. Near the solidus of the system (about 1,250 °C) KCpx contains up to 5.6 wt% of K2O, i.e. about 22–26 mol% of KAlSi2O6. Such high concentration of potassium in KCpx is presumably the maximal content of KAlSi2O6 in the Fe-free clinopyroxene at 7 GPa. In addition to the major substitution MgM1C2Al1K2, the KCpx solid solution contains Ca-Eskola and only minor Ca-Tschermack components. Our experimental results indicate that the natural assemblage KCpx+grossular-rich garnet might be a product of crystallization of the ultra-potassic SiO2-rich alumino-silicate mantle melts (>200 km).Editorial responsibility: J. Hoefs  相似文献   

3.
To examine the effect of KCl-bearing fluids on the melting behavior of the Earth’s mantle, we conducted experiments in the Mg2SiO4–MgSiO3–H2O and Mg2SiO4–MgSiO3–KCl–H2O systems at 5 GPa. In the Mg2SiO4–MgSiO3–H2O system, the temperature of the fluid-saturated solidus is bracketed between 1,200–1,250°C, and both forsterite and enstatite coexist with the liquid under supersolidus conditions. In the Mg2SiO4–MgSiO3–KCl–H2O systems with molar Cl/(Cl + H2O) ratios of 0.2, 0.4, and 0.6, the temperatures of the fluid-saturated solidus are bracketed between 1,400–1,450°C, 1,550–1,600°C, and 1,600–1,650°C, respectively, and only forsterite coexists with liquid under supersolidus conditions. This increase in the temperature of the solidus demonstrates the significant effect of KCl on reducing the activity of H2O in the fluid in the Mg2SiO4–MgSiO3–H2O system. The change in the melting residues indicates that the incongruent melting of enstatite (enstatite = forsterite + silica-rich melt) could extend to pressures above 5 GPa in KCl-bearing systems, in contrast to the behavior in the KCl-free system.  相似文献   

4.
A new pyroxene with formula (Na0.86Mg0.14)(Mg0.57Ti0.43)Si2O6, synthesized in a high-pressure toroidal ‘anvil-with-hole’ apparatus at P = 7 GPa and T = 1700 °C, was characterized by X-ray single-crystal diffraction and Raman spectroscopy. The compound was found to be monoclinic (R1 = 2.56 %), space group C2/c, with lattice parameters a = 9.687(2), b = 8.814(1), c = 5.290(1) Å, β = 107.853(2)°, V = 430.08(1) Å3. The coexistence of Mg and Ti4+ at the M1 site does not induce strong modifications either to the M1 site or to the adjacent M2 site. The Raman spectrum of synthetic Na–Ti-pyroxene was obtained for the first time and compared with that of Mg2Si2O6 (with very low concentrations of Na and Ti). The structural characterization of the Na–Ti–Mg-pyroxene is important, because the study of its thermodynamic constants provides new constraints on thermobarometry of the upper mantle assemblages.  相似文献   

5.
Calcium sulfate (CaSO4), one of the major sulfate minerals in the Earth’s crust, is expected to play a major role in sulfur recycling into the deep mantle. Here, we investigated the crystal structure and phase relation of CaSO4 up to ~90 GPa and 2300 K through a series of high-pressure experiments combined with in situ X-ray diffraction. CaSO4 forms three thermodynamically stable polymorphs: anhydrite (stable below 3 GPa), monazite-type phase (stable between 3 and ~13 GPa) and barite-type phase (stable up to at least 93 GPa). Anhydrite to monazite-type phase transition is induced by pressure even at room temperature, while monazite- to barite-type transition requires heating at least to 1500 K at ~20 GPa. The barite-type phase cannot always be quenched from high temperature and is distorted to metastable AgMnO4-type structure or another modified barite structure depending on pressure. We obtained the pressure–volume data and density of anhydrite, monazite- and barite-type phases and found that their densities are lower than those calculated from the PREM model in the studied P–T conditions. This suggests that CaSO4 is gravitationally unstable in the mantle and fluid/melt phase into which sulfur dissolves and/or sulfate–sulfide speciation may play a major role in the sulfur recycling into the deep Earth.  相似文献   

6.
Experimental data are presented for the solubility of NaNbO3 in the ternary system CaCO3–CaF2–NaNbO3 (or calcite–fluorite–lueshite) over the temperature range 500–1,000°C at 0.1 GPa pressure. Liquidus to solidus phase relationships are given for the pseudo-binary join ([CaCO3]60[CaF2]40)100-x–(NaNbO3)x (0<x<60 wt%). These data show that the maximum solubility of NaNbO3 in these liquids is about 17 wt% (or 13.8 wt% Nb2O5) at approximately 930°C, and is represented by the appearance of pyrochlore as the primary liquidus phase. The sub-liquidus assemblages with decreasing temperature for NaNbO3 contents of 20–50 wt% are: pyrochlore + liquid; pyrochlore + CaF2 + liquid; pyrochlore + CaF2 + CaCO3 + liquid. The solidus assemblage is pyrochlore + CaF2 + CaCO3 at temperatures of approximately 700°C (20 wt% NaNbO3) and 600°C (40 wt% NaNbO3). NaNbO3 is present only in sub-solidus assemblages. These data show that in this fluorine-bearing anhydrous system pyrochlore is the principal Nb-hosting supra-solidus phase, in contrast to fluorine-free hydrous melts from which perovskite-structured compounds crystallize. The crystallization of pyrochlore and/or perovskite-structured compounds from haplocarbonatite liquids is thus considered to be dependent upon the F/OH ratio of the melt.  相似文献   

7.
The join CaMgSi2O6–KAlSi3O8 has been studied at 6 GPa (890–1,500°C) and 3.5 GPa (1,000–1,100°C). K-rich melts in the join produce assemblages Cpx + Grt, Cpx + Opx, Cpx + San, and Cpx + Grt + San at 1,100–1,300°C. At NSansystem<~70 mol%, sanidine is unstable on the solidus and appears at the liquidus, if NSansystem>90 mol%. This explains a scarcity of San in mantle Cpx-rich assemblages and its association with high-K aluminosilicate melt inclusions in diamonds. In absence of San, KCpx is the only host for potassium. The K-jadeite content in KCpx systematically increases with decreasing temperature and reaches 10–12 mol% near the solidus. However, KCpx coexists with San at NSansystem>70 mol% and <1,300°C, being formed via reaction San + L=KCpx. The KJd content in KCpx is controlled by the equilibrium San=KJd + SiO2L that displaces to the right with increasing pressure and decreasing both the temperature and This equilibrium is considered to be responsible for the formation of San lamellae in natural UHP Cpx. In our experiments at 3.5 GPa, garnet is absent whereas the KJd and Ca-Eskola contents in Cpx are low, and the join CaMgSi2O6–KAlSi3O8 is close to binary (with the eutectic Cpx + San + L). Different topologies of the join at 6 and 3.5 GPa define a sequence of mineral crystallization from K-rich aluminosilicate melts during cooling and decompression: from KCpx + Grt without San at P>4 GPa to Cpx + San at P<4 GPa. Similar sequence of assemblages is observed in some eclogitic xenoliths from kimberlites and Grt–Cpx rocks of the Kokchetav Complex (Northern Kazakhstan).  相似文献   

8.
Elastic and thermoelastic constants of large single crystals of Ca2MgSi2O7 and Ca2ZnSi2O7 have been derived from ultrasonic resonance frequencies of plane-parallel plates and their shift upon variation of temperature, respectively. In addition, coefficients of thermal expansion and dielectric constants were determined. Both species possess quite similar properties. As observed in other isotypic magnesium and zinc compounds, the mean elastic stiffness and the deviation from the Cauchy relations are significantly larger in the zinc compound, due to a covalent contribution of the Zn–O bond. Positive thermoelastic constants T44 and T66 in Ca2MgSi2O7 allow temperature-independent ultrasonic generators and oscillators to be manufactured.  相似文献   

9.
Thermophysical properties of the various polymorphs (i.e. α-, β- and γ) of Mg2SiO4 were computed with the CRYSTAL06 code within the framework of CO-LCAO-GTF approach by using the hybrid B3LYP density functional method. Potential wells were calculated through a symmetry preserving, variable cell-shape structure relaxation procedure. Vibrational frequencies were computed at the long-wavelength limit corresponding to the center of the Brillouin zone (k → 0). Thermodynamic properties were estimated through a semiclassical approach that combines B3LYP vibrational frequencies for optic modes and the Kieffer’s model for the dispersion relation of acoustic modes. All computed values except volume (i.e. electronic energy, zero point energy, optical vibrational modes, thermal corrections to internal energy, standard state enthalpy and Gibbs free energy of reaction, bulk modulus and its P and T derivatives, entropy, C V, C P) are consistent with available experimental data and/or reasonable estimates. Volumes are slightly overestimated relative to those determined directly by X-ray diffraction. A set of optimized volumetric properties that are consistent with the other semiclassical properties of the phases α, β and γ have been derived by optimization procedure such that the calculated boundaries for the α/β and β/γ equilibria have the best overall agreement with the experimental data for these transitions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.
G. OttonelloEmail:
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10.
In situ high-pressure synchrotron X-ray diffraction and Raman spectroscopic studies of orthorhombic CaFe2O4-type β-CaCr2O4 chromite were carried out up to 16.2 and 32.0 GPa at room temperature using multi-anvil apparatus and diamond anvil cell, respectively. No phase transition was observed in this study. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a zero-pressure volume of V 0 = 286.8(1) Å3, an isothermal bulk modulus of K 0 = 183(5) GPa and the first pressure derivative of isothermal bulk modulus K 0′ = 4.1(8). Analyses of axial compressibilities show anisotropic elasticity for β-CaCr2O4 since the a-axis is more compressible than the b- and c-axis. Based on the obtained and previous results, the compressibility of several CaFe2O4-type phases was compared. The high-pressure Raman spectra of β-CaCr2O4 were analyzed to determine the pressure dependences and mode Grüneisen parameters of Raman-active bands. The thermal Grüneisen parameter of β-CaCr2O4 is determined to be 0.93(2), which is smaller than those of CaFe2O4-type CaAl2O4 and MgAl2O4.  相似文献   

11.
In this project, the oxidation of SO2 pollutant by Mn/Iranian hematite (Mn/IH) as a novel nanocatalyst in aqueous solution was investigated and followed by conductometry in a semi-batch reactor. The removal of SO2 gas is very important for decreasing the environmental pollution. The Mn/IH was prepared by coprecipitation method, and a novel way was used for converting SO2 to sulfuric acid as an energy source. The characterization of catalyst was determined by X-ray diffraction, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy and X-ray fluorescence techniques. A Box–Behnken design was used to reduce the number of test runs and optimize the influencing factors such as the amount of nanocatalyst, temperature and the reaction time in oxidation of SO2. The graphical counter plots and response surface were used to determine the optimum conditions. Analysis of variance showed a high determination coefficient value (\(R^{2} = 0.9999\), \(R_{\text{adj}}^{2} = 0.9996\) and \(R_{\text{pred}}^{2} = 0.9980\) for oxidation of SO2) and satisfactory prediction second-order regression model. Based on the optimum results, the maximum efficiency for oxidation of SO2 was 90.67%, and it was achieved at initial temperature of 286.03 K, concentration of Mn/IH at 951.11 mg/l and 35.75 min of reaction. The results showed that the temperature had the most significant effect on SO2 oxidation compared with the other two variables.  相似文献   

12.
Six synthetic NaScSi2O6–CaNiSi2O6 pyroxenes were studied by optical absorption spectroscopy. Five of them of intermediate (Na1−x , Ca x )(Sc1−x , Ni x )Si2O6 compositions show spectra typical of Ni2+ in octahedral coordination, more precise Ni2+ at the M1 site of the pyroxene structure. The common feature of all spectra is three broad absorption bands with maxima around 8,000, 13,000 and 24,000 cm−1 assigned to 3 A 2g → 3 T 2g, 3 A 2g → 3 T 1g and →3 T 1g (3 P) electronic spin-allowed transitions of VINi2+. A weak narrow peak at ∼14,400 cm−1 is assigned to the spin-forbidden 3 A 2g → 1 T 2g (1 D) transition of Ni2+. Under pressure the spin-allowed bands shift to higher energies and change in intensity. The octahedral compression modulus, calculated from the shift of the 3 A 2g → 3 T 2g band in the (Na0.7Ca0.3)(Sc0.7Ni0.3)Si2O6 pyroxene is evaluated as 85±20 GPa. The Racah parameter B of Ni2+(M1) is found gradually changing from ∼919 cm−1 at ambient pressure to ∼890 cm−1 at 6.18 GPa. The Ni end-member pyroxene [(Ca0.93 Ni0.07)NiSi2O6] has a spectrum different from all others. In addition to the above mentioned bands of Ni2+(M1) it displays several new relatively intense and broad extra bands, which were attributed to electronic transitions of Ni2+ at the M2 site. In difference to CaO8 polyhedron geometry of an eightfold coordination, Ni2+(M2)O8 polyhedra are assumed to be relatively large distorted octahedra. Due to different distortions and different compressibilities of the M1 and M2 sites the Ni2+(M1)- and Ni2+(M2)-bands display rather different pressure-induced behaviors, becoming more resolved in the high-pressure spectra than in that measured at atmospheric pressure. The octahedral compression modulus of Ni2+(M1) in this end-member pyroxene is evaluated as 150 ± 25 GPa, which is noticeably larger than in Ni0.3 pyroxene. This is due to a smaller size and, thus, a stiffer character of Ni2+(M1)O6 octahedron in the (Ca0.93Ni0.07)NiSi2O6 pyroxene compared to (Na0.7Ca0.3)(Sc0.7Ni0.3)Si2O6.
Monika Koch-MüllerEmail:
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13.
Reactions and partial melting of peraluminous rocks in the presence of H2O-CO2–salt fluids under parameters of granulite-facies metamorphism were modeled in experiments on interaction between orthopyroxene–cordierite–biotite–plagioclase–quartz metapelite with H2O, H2O-CO2, H2O-CO2-NaCl, and H2O-CO2-KCl fluids at 600 MPa and 850°C. Rock melting in the presence of H2O and equimolar H2O-CO2 fluids generates peraluminous (A/CNK1 > 1.1) melts whose composition corresponds to magnesian calcic or calc–alkaline S-type granitoids. The melts are associated with peritectic phases: magnesian spinel and orthopyroxene containing up to 9 wt % Al2O3. In the presence of H2O-CO2-NaCl fluid, cordierite and orthopyroxene are replaced by the association of K-Na biotite, Na-bearing gedrite, spinel, and albite. The Na2O concentrations in the biotite and gedrite are functions of the NaCl concentrations in the starting fluid. Fluids of the composition H2O-CO2-KCl induce cordierite replacement by biotite with corundum and spinel and by these phases in association with potassium feldspar at X KCl = 0.02 in the fluid. When replaced by these phases, cordierite is excluded from the melting reactions, and the overall melting of the metapelite is controlled by peritectic reactions of biotite and orthopyroxene with plagioclase and quartz. These reactions produce such minerals atypical of metapelites as Ca-Na amphibole and clinopyroxene. The compositions of melts derived in the presence of salt-bearing fluids are shifted toward the region with A/CNK < 1.1, as is typical of so-called peraluminous granites of type I. An increase in the concentrations of salts in the fluids leads to depletion of the melts in Al2O3 and CaO and enrichment in alkalis. These relations suggest that the protoliths of I-type peraluminous granites might have been metapelites that were melted when interacting with H2O-CO2-salt fluids. The compositions of the melts can evolve from those with A/CNK > 1.1 (typical of S-type granites) toward those with A/CNK = 1.0–1.1 in response to an increase in the concentrations of alkali salts in the fluids within a few mole percent. Our experiments demonstrate that the origin of new mineral assemblages in metapelite in equilibrium with H2O-CO2-salt fluids is controlled by the activities of alkaline components, while the H2O and CO2 activities play subordinate roles. This conclusion is consistent with the results obtained by simulating metapelite mineral assemblages by Gibbs free energy minimization (using the PERPE_X software), as shown in log(\({a_{{H_2}O}}\))–log(\({a_{N{a_2}O}}\)) and log(\({a_{{H_2}O}}\))–log(\({a_{{K_2}O}}\)) diagrams.  相似文献   

14.
The high-pressure behavior of -Fe2O3 has been studied under static compression up to 60 GPa, using a laser-heated diamond anvil cell. Synchrotron-based angular-dispersive X-ray diffraction shows that the sample remains in the corundum structure up to 50 GPa, but with the appearance of coexisting diffraction lines from a high-pressure phase at pressures above 45 GPa. A least-squares fit of low-pressure phase data to an Eulerian finite-strain equation of state yields linear incompressibilities of K a 0=749.5 (± 18.4) GPa and K c 0= 455.7 (± 21.4) GPa, differing by a factor of 1.6 along the two directions. The enhanced compressibility of the c axis may lead to breaking of vertex- or edge-sharing bonds between octahedra, inducing the high-pressure phase transformation at 50 GPa. Analysis of linear compressibilities suggests that the high-pressure phase above 50 GPa is of the Rh2O3 (II) structure. Continuous laser heating reveals a new structural phase transformation of -Fe2O3 at 22 GPa, to an orthorhombic structure with a=7.305(3) Å, b=7.850(3) Å, and c=12.877(14) Å, different from the Rh2O3 (II) structure.  相似文献   

15.
Thermal behaviour of γ-anhydrite (γ-CaSO4, soluble anhydrite) has been investigated in situ real-time using laboratory parallel-beam X-ray powder diffraction data. Thermal expansion has been analysed from 303 to 569 K with temperature steps of 4 K. Lattice parameters and volume were fitted with a second-order polynomial to calculate thermal expansion coefficients. Thermal expansion of γ-anhydrite is anisotropic being larger along the c axis. Within the 343–383 K thermal range, γ-anhydrite has been found to partially re-hydrate to bassanite CaSO4·0.5H2O. At 455 K the transformation γ-CaSO4 → β-CaSO4, insoluble anhydrite, starts reaching completion at 653 K.  相似文献   

16.
Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe4O5–Mg2Fe2O5 solid solutions and (2) to explore the phase relations involving (Mg,Fe)2Fe2O5 (denoted as O5-phase) and Mg–Fe silicates. Multi-anvil experiments were performed at 11–20 GPa and 1100–1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O5-phase coexists with Fe2O3, hp-(Mg,Fe)Fe2O4, (Mg,Fe)3Fe4O9 or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O5-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe3+-bearing phase B. However, (Mg,Fe)2Fe2O5 does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe2+ and Fe3+ (at least ~?1.0 cations Fe per formula unit). Fe-L2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe3+/Fetot?=?~?0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si4+?+?[6]Mg2+?=?2Fe3+. The ability to accommodate Fe2+ and Fe3+ makes this potential “water-storing” mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg2Fe2O5 have been refined, yielding H°1bar,298?=???1981.5 kJ mol??1. Solid solution is complete across the Fe4O5–Mg2Fe2O5 binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe2+ with silicates indicates that (Mg,Fe)2Fe2O5 has a strong preference for Fe2+. Modelling of partitioning with olivine is consistent with the O5-phase exhibiting ideal mixing behaviour. Mg–Fe2+ partitioning between (Mg,Fe)2Fe2O5 and ringwoodite or wadsleyite is influenced by the presence of Fe3+ and OH incorporation in the silicate phases.  相似文献   

17.
Synthesis experiments in the system MgAl2O4–MgFe2O4 [MgAl2–xFexO4 (0 x 2)] were carried out using a PbF2 flux. The crystalline products synthesized in the compositional range of 0.6 <x 1.2 consisted of two spinel phases, whereas those synthesized in the compositional ranges of 0.0 x 0.6 and 1.2 < x 2.0 crystallized as single spinel phases. Structure refinements of the spinel single crystals, which grew in the ranges of 0.0 x 0.6 and 1.2 < x 2.0, show that the degree of randomness of cation distribution between A and B sites increases as x approaches the two-phase region. This means that the degree of the size mismatch among Mg2+, Fe3+ and Al3+occupying each equivalent mixing site increases as x approaches the two-phase region. Consequently, if the coexistence of two spinels observed in the intermediate compositions reveals the existence of a miscibility gap at low temperatures, this increase in the degree of the size mismatch among the three cations is suggested as a factor of energetic destabilization to form the miscibility gap.  相似文献   

18.
We have collected high resolution neutron powder diffraction patterns from Na2SO4·10D2O over the temperature range 4.2–300 K following rapid quenching in liquid nitrogen, and over a series of slow warming and cooling cycles. The crystal is monoclinic, space-group P21/c (Z = 4) with a = 11.44214(4) Å, b = 10.34276(4) Å, c = 12.75486(6) Å, β = 107.847(1)°, and V = 1436.794(8) Å3 at 4.2 K (slowly cooled), and a = 11.51472(6) Å, b = 10.36495(6) Å, c = 12.84651(7) Å, β = 107.7543(1)°, V = 1460.20(1) Å3 at 300 K. Structures were refined to R P (Rietveld powder residual, \( R_{P} = {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } \mathord{\left/ {\vphantom {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } {\sum {I_{\text{obs}} } }}} \right. \kern-\nulldelimiterspace} {\sum {I_{\text{obs}} } }} \)) better than 2.5% at 4.2 K (quenched and slow cooled), 150 and 300 K. The sulfate disorder observed previously by Levy and Lisensky (Acta Cryst B34:3502–3510, 1978) was not present in our specimen, but we did observe changes with temperature in deuteron occupancies of the orientationally disordered water molecules coordinated to Na. The temperature dependence of the unit-cell volume from 4.2 to 300 K is well represented by a simple polynomial of the form V = ? 4.143(1) × 10?7 T 3 + 0.00047(2) T2 ? 0.027(2) T + 1437.0(1) Å3 (R 2 = 99.98%). The coefficient of volume thermal expansion, α V , is positive above 40 K, and displays a similar magnitude and temperature dependence to α V in deuterated epsomite and meridianiite. The relationship between the magnitude and orientation of the principal axes of the thermal expansion tensor and the main structural elements are discussed; freezing in of deuteron disorder in the quenched specimen affects the thermal expansion, manifested most obviously as a change in the behaviour of the unit-cell parameter β.  相似文献   

19.
Brackets on the melting temperature of K2CO3 were experimentally determined at 1.86 ± 0.02 GPa (1,163–1,167°C), 2.79 ± 0.03 GPa (1,187–1,195°C), and 3.16 ± 0.04 GPa (1,183–1,189°C) in a piston-cylinder apparatus. These new data, in combination with published experiments at low pressure (<0.5 GPa), establish the K2CO3 fusion curve to 3.2 GPa. On the basis of these experiments and published thermodynamic data for crystalline and liquid K2CO3, the high-pressure density and compressibility of K2CO3 liquid were derived from the fusion curve. The pressure dependence of the liquid compressibility (K′0 = dK 0/dP, where K 0 = 1/β0) is between 16.2 and 11.6, with a best estimate of 13.7, in a third-order Birch–Murnaghan equation of state (EOS). This liquid K′0 leads to a density of 2,175 ± 36 kg/m3 at 4 GPa and 1,500°C, which is ∼30% lower than that reported in the literature on the basis of the falling-sphere method at the same conditions. The uncertainty in the liquid K′0 leads to an error in melt density of ± 2% at 4 GPa; the error decreases with decreasing pressure. With a K′0 of 13.7, the compressibility of K2CO3 at 1,500°C and 1 bar (K 0 = 3.8 GPa) drops rapidly with increasing pressure ( ), which prevents a density crossover with silicate melts, such as CaAlSi2O8 and CaMgSi2O6, at upper mantle depths.  相似文献   

20.
We have experimentally investigated the kinetics of melting of an aplitic leucogranite (quartz+sodic plagioclase of ≈Ab90+K-feldspar+traces of biotite) at 690, 740, and 800°C, all at 200 MPa H2O. Leucogranite cylinders, 3.5 mm in diameter and 7 mm in length, were run in the presence of excess H2O using cold-seal pressure vessels for 11–2,925 h. At 690 and 740°C and any experimental time, and 800°C and short run times, silicate glass (melt at run conditions) occurs as interconnected films along most of the mineral boundaries and in fractures, with the predominant volume occurring along quartz/feldspars boundaries and quartz/plagioclase/K-feldspar triple junctions. Glass film thickness is roughly constant throughout a given experimental charge and increases with experimental temperature and run duration. The results indicate that H2O-saturated partial melting of a quartzo-feldspathic protolith will produce an interconnected melt phase even at very low degrees (<5 vol%) of partial melting. Crystal grain boundaries are therefore completely occluded with melt films even at the lowest degrees of partial melting, resulting in a change in the mechanism of mass transport through the rock from advection of aqueous vapor to diffusion through silicate melt. At 690 and 740°C the compositions of glasses are homogeneous and (at both temperatures) close to, but not on, the H2O-saturated 200 MPa haplogranite eutectic; glass compositions do not change with run duration. At 800°C glasses are heterogeneous and plot away from the minimum, although their molar ratios ASI (=mol Al2O3/CaO+Na2O+K2O) and Al/Na are constant throughout the entire charge at any experimental time. Glass compositions within individual 800°C experiments form linear trends in (wt%) normative quartz–albite–orthoclase space. The linear trends are oriented perpendicular to the 200 MPa H2O haplogranite cotectic line, reflecting nearly constant albite/orthoclase ratio versus variable quartz/feldspar ratio, and have endpoints between the 800°C isotherms on the quartz and feldspar liquidus surfaces. With increasing experimental duration the trends migrate from the potassic side of the minimum toward the bulk rock composition located on the sodic side, due to more rapid (and complete) dissolution of K-feldspar relative to plagioclase. The results indicate that partial melting at or slightly above the solidus (690–740°C) is interface reaction-controlled, and produces disequilibrium melts of near-minimum composition that persist metastably for up to at least 3 months. Relict feldspars show no change in composition or texture, and equilibration between melt and feldspars might take from a few to tens of millions of years. Partial melting at temperatures well above the solidus (800°C) produces heterogeneous, disequilibrium liquids whose compositions are determined by the diffusive transport properties of the melt and local equilibrium with neighboring mineral phases. Feldspars recrystallize and change composition rapidly. Partial melting and equilibration between liquids and feldspars might take from a few to tens of years (H2O-saturated conditions) at these temperatures well above the solidus.  相似文献   

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