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1.
Raman spectroscopy and heat capacity measurements have been used to study the post-perovskite phase of CaIr0.5Pt0.5O3, recovered from synthesis at a pressure of 15 GPa. Laser heating CaIr0.5Pt0.5O3 to 1,900 K at 60 GPa produces a new perovskite phase which is not recoverable and reverts to the post-perovskite polymorph between 20 and 9 GPa on decompression. This implies that Pt-rich CaIr1−xPtxO3 perovskites including the end member CaPtO3 cannot easily be recovered to ambient pressure from high P–T synthesis. We estimate an increase in the thermodynamic Grüneisen parameter across the post-perovskite to perovskite transition of 34%, of similar magnitude to those for (Mg,Fe)SiO3 and MgGeO3, suggesting that CaIr0.5Pt0.5O3 is a promising analogue for experimental studies of the competition in energetics between perovskite and post-perovskite phases of magnesium silicates in Earth’s lowermost mantle. Low-temperature heat capacity measurements show that CaIrO3 has a significant Sommerfeld coefficient of 11.7 mJ/mol K2 and an entropy change of only 1.1% of Rln2 at the 108 K Curie transition, consistent with the near-itinerant electron magnetism. Heat capacity results for post-perovskite CaIr0.5Rh0.5O3 are also reported.  相似文献   

2.
KAlSi3O8 sanidine dissociates into a mixture of K2Si4O9 wadeite, Al2SiO5 kyanite and SiO2 coesite, which further recombine into KAlSi3O8 hollandite with increasing pressure. Enthalpies of KAlSi3O8 sanidine and hollandite, K2Si4O9 wadeite and Al2SiO5 kyanite were measured by high-temperature solution calorimetry. Using the data, enthalpies of transitions at 298 K were obtained as 65.1 ± 7.4 kJ mol–1 for sanidine wadeite + kyanite + coesite and 99.3 ± 3.6 kJ mol–1 for wadeite + kyanite + coesite hollandite. The isobaric heat capacity of KAlSi3O8 hollandite was measured at 160–700 K by differential scanning calorimetry, and was also calculated using the Kieffer model. Combination of both the results yielded a heat-capacity equation of KAlSi3O8 hollandite above 298 K as Cp=3.896 × 102–1.823 × 103T–0.5–1.293 × 107T–2+1.631 × 109T–3 (Cp in J mol–1 K–1, T in K). The equilibrium transition boundaries were calculated using these new data on the transition enthalpies and heat capacity. The calculated transition boundaries are in general agreement with the phase relations experimentally determined previously. The calculated boundary for wadeite + kyanite + coesite hollandite intersects with the coesite–stishovite transition boundary, resulting in a stability field of the assemblage of wadeite + kyanite + stishovite below about 1273 K at about 8 GPa. Some phase–equilibrium experiments in the present study confirmed that sanidine transforms directly to wadeite + kyanite + coesite at 1373 K at about 6.3 GPa, without an intervening stability field of KAlSiO4 kalsilite + coesite which was previously suggested. The transition boundaries in KAlSi3O8 determined in this study put some constraints on the stability range of KAlSi3O8 hollandite in the mantle and that of sanidine inclusions in kimberlitic diamonds.  相似文献   

3.
The crystal structure of the unstable mineral alumoklyuchevskite K3Cu3AlO2(SO4)4 [monoclinic, I2, a = 18.772(7), b = 4.967(2), c = 18.468(7) Å, β = 101.66(1)°, V = 1686(1) Å] was refined to R 1 = 0.131 for 2450 unique reflections with F ≥ 4σF hkl. The structure is based on oxocentered tetrahedrons (OAlCu 3 7+ ) linked into chains via edges. Each chain is surrounded by SO4 tetrahedrons forming a structural complex. Each complex is elongated along the b axis. This type of crystal structure was also found in other fumarole minerals of the Great Tolbachik Fissure Eruption (GTFE, Kamchatka Peninsula, Russia, 1975–1976), klyuchevskite, K3Cu3Fe3+O2(SO4)4; and piypite, K2Cu2O(SO4)2.  相似文献   

4.
Pyrrhotite (Fe7S8) is a natural iron sulphide that can participate in rock magnetisation. Its electronic structure is not yet surely described. X-ray magnetic circular dichroism (XMCD) at Fe L2,3 edges on Fe7S8, coupled with multiplet calculations, shows that iron is present only as Fe2+ in this magnetic iron sulphide. It reveals a strong magnetic orbital moment. XMCD at Fe and S K edges shows the quite strong polarization of both Fe and S in Fe7S8.  相似文献   

5.
We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl2O4 and MgCr2O4. The data also include new low-temperature heat capacity measurements for MgAl2O4 spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results. No heat capacity anomaly was observed for MgAl2O4 spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)2O4 spinels. We suggest a standard entropy for MgAl2O4 of 80.9 ± 0.6 J mol−1 K−1. For the solid solution between MgAl2O4 and MgCr2O4, we observe a linear increase of the standard entropies from 80.9 J mol−1 K−1 for MgAl2O4 to 118.3 J mol−1 K−1 for MgCr2O4.  相似文献   

6.
Stabilities of hexagonal new aluminous (NAL) phase and Ca-ferrite-type (CF) phase were investigated on the join NaAlSiO4-MgAl2O4 in a pressure range from 23 to 58 GPa at approximately constant temperature of 1,850 K, on the basis of in situ synchrotron X-ray diffraction measurements in a laser-heated diamond-anvil cell. The results show that NAL is formed as a single phase up to 34 GPa, NAL + CF between 34 and 43 GPa, and only CF at higher pressures in 40%NaAlSiO4-60%MgAl2O4 bulk composition. On the other hand, both NAL and CF coexist below 38 and 36 GPa, and only CF was obtained at higher pressures in 60%NaAlSiO4-40%MgAl2O4 and 20%NaAlSiO4-80%MgAl2O4 composition, respectively. These results indicate that NAL appears only up to 46 GPa at 1,850 K, and CF forms continuous solid solution at higher pressures on the join NaAlSiO4-MgAl2O4. NAL has limited stability in subducted mid-oceanic ridge basalt crust in the Earth’s lower mantle and undergoes a phase transition to CF in deeper levels.  相似文献   

7.
 Synthetic aegirine LiFeSi2O6 and NaFeSi2O6 were characterized using infrared spectroscopy in the frequency range 50–2000 cm−1, and at temperatures between 20 and 300 K. For the C2/c phase of LiFeSi2O6, 25 of the 27 predicted infrared bands and 26 of 30 predicted Raman bands are recorded at room temperature. NaFeSi2O6 (with symmetry C2/c) shows 25 infrared and 26 Raman bands. On cooling, the C2/c–P21/c structural phase transition of LiFeSi2O6 is characterized by the appearance of 13 additional recorded peaks. This observation indicates the enlargement of the unit cell at the transition point. The appearance of an extra band near 688 cm−1 in the monoclinic P21/c phase, which is due to the Si–O–Si vibration in the Si2O6 chains, indicates that there are two non-equivalent Si sites with different Si–O bond lengths. Most significant spectral changes appear in the far-infrared region, where Li–O and Fe–O vibrations are mainly located. Infrared bands between 300 and 330 cm−1 show unusually dramatic changes at temperatures far below the transition. Compared with the infrared data of NaFeSi2O6 measured at low temperatures, the change in LiFeSi2O6 is interpreted as the consequence of mode crossing in the frequency region. A generalized Landau theory was used to analyze the order parameter of the C2/c–P21/c phase transition, and the results suggest that the transition is close to tricritical. Received: 21 January 2002 / Accepted: 22 July 2002  相似文献   

8.
The crystal structure of Pb6Bi2S9 is investigated at pressures between 0 and 5.6 GPa with X-ray diffraction on single-crystals. The pressure is applied using diamond anvil cells. Heyrovskyite (Bbmm, a = 13.719(4) Å, b = 31.393(9) Å, c = 4.1319(10) Å, Z = 4) is the stable phase of Pb6Bi2S9 at ambient conditions and is built from distorted moduli of PbS-archetype structure with a low stereochemical activity of the Pb2+ and Bi3+ lone electron pairs. Heyrovskyite is stable until at least 3.9 GPa and a first-order phase transition occurs between 3.9 and 4.8 GPa. A single-crystal is retained after the reversible phase transition despite an anisotropic contraction of the unit cell and a volume decrease of 4.2%. The crystal structure of the high pressure phase, β-Pb6Bi2S9, is solved in Pna2 1 (a = 25.302(7) Å, b = 30.819(9) Å, c = 4.0640(13) Å, Z = 8) from synchrotron data at 5.06 GPa. This structure consists of two types of moduli with SnS/TlI-archetype structure in which the Pb and Bi lone pairs are strongly expressed. The mechanism of the phase transition is described in detail and the results are compared to the closely related phase transition in Pb3Bi2S6 (lillianite).  相似文献   

9.
Atomistic model was proposed to describe the thermodynamics of mixing in the diopside-K-jadeite solid solution (CaMgSi2O6-KAlSi2O6). The simulations were based on minimization of the lattice energies of 800 structures within a 2 × 2 × 4 supercell of C2/c diopside with the compositions between CaMgSi2O6 and KAlSi2O6 and with variable degrees of order/disorder in the arrangement of Ca/K cations in M2 site and Mg/Al in Ml site. The energy minimization was performed with the help of a force-field model. The results of the calculations were used to define a generalized Ising model, which included 37 pair interaction parameters. Isotherms of the enthalpy of mixing within the range of 273–2023 K were calculated with a Monte Carlo algorithm, while the Gibbs free energies of mixing were obtained by thermodynamic integration of the enthalpies of mixing. The calculated T-X diagram for the system CaMgSi2O6-KAlSi2O6 at temperatures below 1000 K shows several miscibility gaps, which are separated by intervals of stability of intermediate ordered compounds. At temperatures above 1000 K a homogeneous solid solution is formed. The standard thermodynamic properties of K-jadeite (KAlSi2O6) evaluated from quantum mechanical calculations were used to determine location of several mineral reactions with the participation of the diopside-K-jadeite solid solution. The results of the simulations suggest that the low content of KalSi2O6 in natural clinopyroxenes is not related to crystal chemical factors preventing isomorphism, but is determined by relatively high standard enthalpy of this end member.  相似文献   

10.
A single crystal X-ray diffraction study on lithium tetraborate Li2B4O7 (diomignite, space group I41 cd) has been performed under pressure up to 8.3 GPa. No phase transitions were found in the pressure range investigated, and hence the pressure evolution of the unit-cell volume of the I41 cd structure has been described using a third-order Birch–Murnaghan equation of state (BM-EoS) with the following parameters: V 0  = 923.21(6) Å3, K 0  = 45.6(6) GPa, and K′ = 7.3(3). A linearized BM-EoS was fitted to the axial compressibilities resulting in the following parameters a 0  = 9.4747(3) Å, K 0a  = 73.3(9) GPa, K′ a  = 5.1(3) and c 0  = 10.2838(4) Å, K 0c  = 24.6(3) GPa, K′ c  = 7.5(2) for the a and c axes, respectively. The elastic anisotropy of Li2B4O7 is very large with the zero-pressure compressibility ratio β 0c /β 0a  = 3.0(1). The large elastic anisotropy is consistent with the crystal structure: A three-dimensional arrangement of relatively rigid tetraborate groups [B4O7]2− forms channels occupied by lithium along the polar c–axis, and hence compression along the c axis requires the shrinkage of the lithium channels, whereas compression in the a direction depends mainly on the contraction of the most rigid [B4O7]2− units. Finally, the isothermal bulk modulus obtained in this work is in general agreement with that derived from ultrasonic (Adachi et al. in Proceedings-IEEE Ultrasonic Symposium, 228–232, 1985; Shorrocks et al. in Proceedings-IEEE Ultrasonic Symposium, 337–340, 1981) and Brillouin scattering measurements (Takagi et al. in Ferroelectrics, 137:337–342, 1992).  相似文献   

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