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1.
K-lingunite is a high-pressure modification of K-feldspar that possesses the tetragonal hollandite structure. Variations of the Raman spectra of K-lingunite were studied up to ~31.5 GPa at room temperature, and in the range 79–823 K at atmospheric pressure. The Raman frequencies of all bands were observed to increase with increasing pressure, and decrease with increasing temperature for K-lingunite. This behavior is in line with those observed for most of other materials. New sharp Raman bands appear at pressures greater than 13–15 GPa, suggesting a phase transition in K-lingunite with increasing pressure. The transition is reversible when pressure was released. The appearance of these new Raman bands may correspond to the phase transition revealed earlier at around 20 GPa by X-ray diffraction studies. Instead of transforming back to its stable minerals, such as orthoclase, microcline or sanidine, K-lingunite became amorphous in the temperature range 803–823 K at atmospheric pressure.  相似文献   

2.
In situ time-resolved measurements of shock wave profiles for anisotropic fluorite crystals with two different crystal orientations were carried out up to a pressure of 34 GPa that is above the transition pressure for the fluorite to cotunnite phase. They indicate that the Hugoniot elastic limit varies with the crystal orientation and final pressure and that high-pressure phase transition from fluorite to a cotunnite-type structure occurs at 13 GPa in 10–20 ns for CaF2 [100]-oriented crystals and at 17 GPa in more than 50 ns for CaF2 [111]-oriented crystals, respectively. These results are in disagreement with those from static compression. The phase transition at static pressures has been known to be very sluggish, but the present results indicate a large sensitivity of kinetics to the relationship between crystallographic orientation and shock direction, supporting a martensitic mechanism for the fluorite to cotunnite phase transition that is enhanced by the effect of shock-induced shear. It is also helpful to explain the observation that the in situ emission spectra for shocked Eu-doped fluorite became weak and had no shift above ~15 GPa.  相似文献   

3.
The high-pressure behavior of the lattice elasticity of spodumene, LiAlSi2O6, was studied by static compression in a diamond-anvil cell up to 9.3 GPa. Investigations by means of single-crystal XRD and Raman spectroscopy within the hydrostatic limits of the pressure medium focus on the pressure ranges around ~3.2 and ~7.7 GPa, which have been reported previously to comprise two independent structural phase transitions. While our measurements confirm the well-established first-order C2/cP21/c transformation at 3.19 GPa (with 1.2% volume discontinuity and a hysteresis between 0.02 and 0.06 GPa), both unit-cell dimensions and the spectral changes observed in high-pressure Raman spectra give no evidence for structural changes related to a second phase transition. Monoclinic lattice parameters and unit-cell volumes at in total 59 different pressure points have been used to re-calculate the lattice-related properties of spontaneous strain, volume strain, and the bulk moduli as a function of pressure across the transition. A modified Landau free energy expansion in terms of a one component order parameter has been developed and tested against these experimentally determined data. The Landau solution provides a much better reproduction of the observed anomalies than any equation-of-state fit to data sets truncated below and above P tr, thus giving Landau parameters of K 0 = 138.3(2) GPa, K′ = 7.46(5), λ V  = 33.6(2) GPa, a = 0.486(3), b = −29.4(6) GPa and c = 551(11) GPa.  相似文献   

4.
Single-crystal X-ray diffraction experiments with SiO2 α-cristobalite reveal that the well-known reversible displacive phase transition to cristobalite-II, which occurs at approximately 1.8 GPa, can be suppressed by rapid pressure increase, leading to an overpressurized metastable state, persisting to pressure as high as 10 GPa. In another, slow pressure increase experiment, the monoclinic high-pressure phase-II was observed to form at ~1.8 GPa, in agreement with earlier in situ studies, and its crystal structure has been unambiguously determined. Single-crystal data have been used to refine the structure models of both phases over the range of pressure up to the threshold of formation of cristobalite X-I at ~12 GPa, providing important constraints on the feasibility of the two competing silica densification models proposed in the literature, based on quantum mechanical calculations. Preliminary diffraction data obtained for cristobalite X-I reveal a monoclinic unit cell that contradicts the currently assumed model.  相似文献   

5.
The fluoroperovskite phase RbCaF3 has been investigated using high-pressure neutron powder diffraction in the pressure range ~0–7.9 GPa at room temperature. It has been found to undergo a first-order high-pressure structural phase transition at ~2.8 GPa from the cubic aristotype phase to a hettotype phase in the tetragonal space group I4/mcm. This transition, which also occurs at ~200 K at ambient pressure, is characterised by a linear phase boundary and a Clapeyron slope of 2.96 × 10?5 GPa K?1, which is in excellent agreement with earlier, low-pressure EPR investigations. The bulk modulus of the high-pressure phase (49.1 GPa) is very close to that determined for the low-pressure phase (50.0 GPa), and both are comparable with those determined for the aristotype phases of CsCdF3, TlCdF3, RbCdF3, and KCaF3. The evolution of the order parameter with pressure is consistent with recent modifications to Landau theory and, in conjunction with polynomial approximations to the pressure dependence of the lattice parameters, permits the pressure variation of the bond lengths and angles to be predicted. On entering the high-pressure phase, the Rb–F bond lengths decrease from their extrapolated values based on a third-order Birch–Murnaghan fit to the aristotype equation of state. By contrast, the Ca–F bond lengths behave atypically by exhibiting an increase from their extrapolated magnitudes, resulting in the volume and the effective bulk modulus of the CaF6 octahedron being larger than the cubic phase. The bulk moduli for the two component polyhedra in the tetragonal phase are comparable with those determined for the constituent binary fluorides, RbF and CaF2.  相似文献   

6.
石英高压相变研究进展   总被引:2,自引:0,他引:2  
罗扬  施旭  贺红亮  赵永红 《地学前缘》2007,14(3):149-157
文中总结了前人有关石英高温高压相变的实验结果。根据以前的实验,在静水压条件下,石英-柯石英-斯石英-CaCl2结构超斯石英相-α-PbO2结构超斯石英相之间的相变方程分别是:p(GPa)=(2.11±0.03)+(9.8×10-4±1.2×10-4)×T(℃),p(GPa)=(8.0±0.2)+(1.1×10-3±3×10-4)×T(℃),p(GPa)=(51±2)+(0.012±0.005)×T(K),p(GPa)=98+(0.0095±0.0016)×T(K)。文中还初步探讨了非静水压状态对石英相变的影响。实验结果表明,差应力的出现降低了石英相变所需要的围压,即相变边界向低压方向偏移,在周永胜等人实验数据的基础上,笔者尝试将二维的相图扩展到三维相图以考虑差应力的影响。最后讨论了石英相变在地学研究中的作用,对比不同的观点分析了前人对超高压变质作用过程的解释,希望可以为以后解释地质资料提供较为广泛的可能性,促进我们对地球内部动力学过程的了解。  相似文献   

7.
We have used density functional theory to investigate the stability of MgAl2O4 polymorphs under pressure. Our results can reasonably explain the transition sequence of MgAl2O4 polymorphs observed in previous experiments. The spinel phase (stable at ambient conditions) dissociates into periclase and corundum at 14 GPa. With increasing pressure, a phase change from the two oxides to a calcium-ferrite phase occurs, and finally transforms to a calcium-titanate phase at 68 GPa. The calcium-titanate phase is stable up to at least 150 GPa, and we did not observe a stability field for a hexagonal phase or periclase + Rh2O3(II)-type Al2O3. The bulk moduli of the phases calculated in this study are in good agreement with those measured in high-pressure experiments. Our results differ from those of a previous study using similar methods. We attribute this inconsistency to an incomplete optimization of a cell shape and ionic positions at high pressures in the previous calculations.  相似文献   

8.
The high-pressure behavior of Keokuk kaolinite has been studied to 9.5 GPa by infrared spectroscopy using synchrotron radiation. The kaolinite-I → kaolinite-II and kaolinite-II → kaolinite-III transformations have clear spectroscopic expression, with discontinuities coinciding with the transformation pressures bracketed by X-ray diffraction (Welch and Crichton in Am Mineral 95:651–654, 2010). The experimental spectra have been interpreted from band assignments derived from density functional theory for the structures of kaolinite-II and kaolinite-III, using as starting models the ab initio structures reported by Mercier and Le Page (Acta Crystallogr A B64:131–143, 2008, Mater Sci Technol 25:437–442, 2009) and unit-cell parameters from Welch and Crichton (Am Mineral 95:651–654, 2010). The relaxed theoretical structures are very similar to those reported by Mercier and Le Page (Acta Crystallogr A B64:131–143, 2008, Mater Sci Technol 25:437–442, 2009) in their theoretical investigation of kaolinite polytypes at high pressure. The vibrational spectra calculated from the quantum-mechanical analysis allow band assignments of the IR spectra to be made and provide insights into the behavior of different OH environments in the two high-pressure polytypes. The single perpendicular-interlayer OH group of kaolinite-III has a distinctive spectroscopic signature that is diagnostic of this polytype (ν = 3,595 cm−1 at 9.5 GPa) and is sensitive to the compression/expansion of the interlayer space. This OH group also has a distinctive signature in the calculated spectra. The spectra collected on decompression are those of kaolinite-III and persist largely unchanged to 4.6 GPa, except for a continuous blue shift of the 3,595 cm−1 band to 3,613 cm−1. Finally, kaolinite-I is recovered at 0.6 GPa, confirming the kaolinite-III → kaolinite-I transformation previously observed by X-ray diffraction, and the irreversibility of the kaolinite-II → kaolinite-III transformation. The ambient spectra collected at the start and finish of the experiment are those of kaolinite-I, and start/finish band frequencies agree to within 6 cm−1.  相似文献   

9.
We have calculated the compressional, vibrational, and thermodynamic properties of Ni3S2 heazlewoodite and the high-pressure orthorhombic phase (with Cmcm symmetry) using the generalized gradient approximation to the density functional theory in conjunction with the quasi-harmonic approximation. The predicted Raman frequencies of heazlewoodite are in good agreement with room-temperature measurements. The calculated thermodynamic properties of heazlewoodite at room conditions agree very well with experiments, but at high temperatures (especially above 500 K) the heat capacity data from experiments are significantly larger than the quasi-harmonic results, indicating that heazlewoodite is anharmonic. On the other hand, the obtained vibrational density of states of the orthorhombic phase at 20 GPa reveals a group of low-frequency vibrational modes which are absent in heazlewoodite. These low-frequency modes contribute substantially to thermal expansivity, heat capacity, entropy, and Grüneisen parameter of the orthorhombic phase. The calculated phase boundary between heazlewoodite and the orthorhombic phase is consistent with high-pressure experiments; the predicted transition pressure is 17.9 GPa at 300 K with a negative Clapeyron slope of −8.5 MPa/K.  相似文献   

10.
Raman spectra of Mg2GeO4-olivine were obtained from ambient pressure up to 34 GPa at ambient temperature. Under quasi-hydrostatic pressure conditions, the following modifications in the Raman spectra occur as pressure increases: 1) near 11 GPa, two sharp extra bands appear in the 600–700 cm?1 frequency range, and increase in intensity with respect to the olivine bands; 2) above 22 GPa, these two bands become very intense, and the number, position and relative intensity of the other vibrational bands drastically change; 3) the intensity of sharp bands progressively decreases above 25 GPa. The transformation occurs at lower pressures under non-hydrostatic conditions. During decompression to atmospheric pressure, the high-pressure phase partially reverts to olivine. These observations can be interpreted as the progressive metastable transformation from the olivine structure to a crystalline phase with four-fold coordinated Ge, in which the GeO4 tetrahedra are polymerized. We propose that the metastable high-pressure phase is a structurally disordered spinelloid close to the hypothethical ω- or ?*-phase, and forms by a shear mechanism assisted by the development of a dynamical instability in the olivine structure. Implications for the transformations undergone by olivines under far-from-equilibrium conditions (e.g. in subducting lithospheric slabs and in shocks) are discussed.  相似文献   

11.
The Raman and Cr3+ and V2+ luminescence spectra of beryl and emerald have been characterized up to 15.0 and 16.4 GPa, respectively. The Raman spectra show that an E 1g symmetry mode at 138 cm?1 shifts negatively by ?4.57 (±0.55) cm?1/GPa, and an extrapolation of the pressure dependence of this mode indicates that a soft-mode transition should occur near 12 GPa. Such a transition is in accord with prior theoretical results. Dramatic changes in Raman mode intensities and positions occur between 11.2 and 15.0 GPa. These changes are indicative of a phase transition that primarily involves tilting and mild distortion of the Si6O18 rings. New Raman modes are not observed in the high-pressure phase, which indicates that the local bonding environment is not altered dramatically across the transition (e.g., changes in coordination do not occur). Both sharp line and broadband luminescence are observed for both Cr3+ and V2+ in emerald under compression to 16.4 GPa. The R-lines of both Cr3+ and V2+ shift to lower energy (longer wavelength) under compression. Both R-lines of Cr3+ split at ~13.7 GPa, and the V2+ R1 slope changes at this pressure and shifts more rapidly up to ~16.4 GPa. The Cr3+ R-line splitting and FWHM show more complex behavior, but also shift in behavior at ~13.7 GPa. These changes in the pressure dependency of the Cr3+ and V2+ R-lines and the changes in R-line splitting and FWHM at ~13.7 GPa further demonstrate that a phase transition occurs at this pressure, in good agreement with our Raman results. The high-pressure phase of beryl appears to have two Al sites that become more regular under compression. Hysteresis is not observed in our Raman or luminescence spectra on decompression, suggesting that this transition is second order in nature: The occurrence of a second-order transition near this pressure is also in accord with prior theoretical results. We speculate that the high-pressure phase (beryl-II) might be a mildly modulated structure, and/or that extensive twinning occurs across this transition.  相似文献   

12.
The pressure-induced A-B phase transition of synthetic Rb-tetra-ferri-annite (Rb-TFA) mica was studied theoretically by means of Density Functional Theory (DFT) method. The calculations show that Rb-TFA keeps a Franzini A-type structure up to at least 5.39 GPa of pressure, whereas at higher pressure, it transforms to a Franzini B-type structure. The negative value of the tetrahedral rotation angle α = −4.68° has appeared at 5.56 GPa of calculated pressure. This result is in a relatively good agreement with experimentally estimated phase transition area in the range of 3.36−3.84 GPa. The energy difference between the A and B structures is very small (ΔE = 8 kJ/mol). The detailed analysis of the optimized structural data shows minimal changes in the structure of Rb-TFA after the pressure-induced phase transition.  相似文献   

13.
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   

14.
We used an in situ measurement method to investigate the phase transition of CaGeO3 polymorphs under high pressures and temperatures. A multi-anvil high-pressure apparatus combined with intense synchrotron X-ray radiation was used. The transition boundary between a garnet and a perovskite phase at T = 900–1,650 K and P = 3–8 GPa was determined as occurring at P (GPa) = 9.0−0.0023 × T (K). The transition pressure determined in our study is in general agreement with that observed in previous high-pressure experiments. The slope, dP/dT, of the transition determined in our study is consistent with that calculated from calorimetry data.  相似文献   

15.
High-pressure and high-temperature experiments conducted in a laser-heated diamond-anvil cell with a synchrotron X-ray diffraction method have revealed a phase transformation in the aragonite-type SrCO3 at pressures above 10 GPa. The new phase has an orthorhombic symmetry and was confirmed to remain stable to 32 GPa. The Birch-Murnaghan equation of state for new phase was determined from the experimental unit cell parameters, with K0 = 101 (± 16) GPa, K0 = 4 (constrained value), and V0 = 111.9 (± 2.2). This transformation in SrCO3 is different from that in BaCO3 as reported in previous studies. After decompression at ambient pressure, the high-pressure phase transforms to a metastable structure, which has an orthorhombic symmetry. This result should also resolve a dispute regarding the stable high-pressure phases in BaCO3, which is an analog material of CaCO3 and SrCO3.This revised version was published in February 2005 with corrections to the Introduction and to the References.  相似文献   

16.
A calorimetric study of the ilmenite and lithium niobate polymorphs of FeTiO3 was undertaken to assess the high-pressure stabilities of these phases. Ilmenite is known to be the stable phase at ambient pressure, but the lithium niobate form may be a quench phase from a perovskite form which has been previously observed in situ at high pressure.In this study, the lithium niobate phase of FeTiO3 was synthesized from an ilmenite starting material at 15– 16 GPa and 1473 K, using a uniaxial split-sphere high-pressure apparatus (USSA 2000). The energetics of the ilmenite to lithium niobate transformation were investigated through transposed-temperature drop calorimetry. The heat of back-transformation of lithium niobate to ilmenite was measured by dropping the sample in argon from ambient conditions to a temperature where the transformation occurs spontaneously. In drops made at 977 K, an intermediate x-ray amorphous phase was encountered. At 1273 K, the transformation went to completion. A value of -13.5±1.2 kJ/mol was obtained for the heat of transformation.  相似文献   

17.
Piston-cylinder experiments on a Pleistocene adakite from Mindanao in the Philippines have been used to establish near-liquidus and sub-liquidus phase relationships relevant to conditions in the East Philippines subduction zone. The experimental starting material belongs to a consanguineous suite of adakitic andesites. Experiments were conducted at pressures from 0.5 to 2 GPa and temperatures from 950 to 1,150°C. With 5 wt. % of dissolved H2O in the starting mix, garnet, clinopyroxene and orthopyroxene are liquidus phases at pressures above 1.5 GPa, whereas clinopyroxene and orthopyroxene are liquidus (or near-liquidus) phases at pressures <1.5 GPa. Although amphibole is not a liquidus phase under any of the conditions examined, it is stable under sub-liquidus conditions at temperature ≤1,050°C and pressures up to 1.5 GPa. When combined with petrographic observations and bulk rock chemical data for the Mindanao adakites, these findings are consistent with polybaric fractionation that initially involved garnet (at pressures >1.5 GPa) and subsequently involved the lower pressure fractionation of amphibole, plagioclase and subordinate clinopyroxene. Thus, the distinctive Y and HREE depletions of the andesitic adakites (which distinguish them from associated non-adakitic andesites) must be established relatively early in the fractionation process. Our experiments show that this early fractionation must have occurred at pressures >1.5 GPa and, thus, deeper than the Mindanao Moho. Published thermal models of the Philippine Sea Plate preclude a direct origin by melting of the subducting ocean crust. Thus, our results favour a model whereby basaltic arc melt underwent high-pressure crystal fractionation while stalled beneath immature arc lithosphere. This produced residual magma of adakitic character which underwent further fractionation at relatively low (i.e. crustal) pressures before being erupted.  相似文献   

18.
《Comptes Rendus Geoscience》2019,351(2-3):243-252
With the application of pressure, a material decreases in volume as described in its equation of state, which is governed by energy considerations. At extreme pressures, common materials are thus expected to transform into new dense phases with extremely compact atomic arrangements that may also have unusual physical properties. For aluminium, first principle calculations have consistently predicted a phase transition sequence fcc–hcp–bcc in a pressure range below 0.5 TPa [1–7]. The hcp phase was identified at 217 GPa in an experiment (Akahama et al., 2006), and the bcc phase has been recently confirmed in a dynamic ramp-compression experiment coupled with time-resolved X-ray diffraction (Polsin et al. 2017). Here we confirm this observation with a synchrotron-based X-ray diffraction experiment carried out within a diamond-anvil cell and report indications of the onset of the transition towards a bcc structure at pressures beyond 320 GPa. With this work, we also demonstrate the possibility of routine static high-pressure experiments with conventional bevelled diamond-anvil geometry in the 0.3–0.4 TPa regime.  相似文献   

19.
《Gondwana Research》2008,13(4):438-453
This paper presents a regional scale observation of metamorphic geology and mineral assemblage variations of Kontum Massif, central Vietnam, supplemented by pressure–temperature estimates and reconnaissance geochronological results. The mineral assemblage variations and thermobarometric results classify the massif into a low- to medium-temperature and relatively high-pressure northern part characterised by kyanite-bearing rocks (570–700 °C at 0.79–0.86 GPa) and a more complex southern part. The southern part can be subdivided into western and eastern regions. The western region shows very high-temperature (> 900 °C) and -pressure conditions characterised by the presence of garnet and orthopyroxene in both mafic and pelitic granulites (900–980 °C at 1.0–1.5 GPa). The eastern region contains widespread medium- to high-temperature and low-pressure rocks, with metamorphic grade increasing from north to south; epidote- or muscovite-bearing gneisses in the north (< 700–740 °C at < 0.50 GPa) to garnet-free mafic and orthopyroxene-free pelitic granulites in the south (790–920 °C at 0.63–0.84 GPa). The Permo-Triassic Sm–Nd ages (247–240 Ma) from high-temperature and -pressure granulites and recent geochronological studies suggest that the south-eastern part of Kontum Massif is composed of a Siluro-Ordovician continental fragment probably showing a low-pressure/temperature continental geothermal gradient derived from the Gondwana era with subsequent Permo-Triassic collision-related high-pressure reactivation zones.  相似文献   

20.
 The second-order elastic constants of CaF2 (fluorite) have been determined by Brillouin scattering to 9.3 GPa at 300 K. Acoustic velocities have been measured in the (111) plane and inverted to simultaneously obtain the elastic constants and the orientation of the crystal. A notable feature of the present inversion is that only the density at ambient condition was used in the inversion. We obtain high-pressure densities directly from Brillouin data by conversion to isothermal conditions and iterative integration of the compression curve. The pressure derivative of the isentropic bulk modulus and of the shear modulus determined in this study are 4.78 ± 0.13 and 1.08 ± 0.07, which differ from previous low-pressure ultrasonic elasticity measurements. The pressure derivative of the isothermal bulk modulus is 4.83 ± 0.13, 8% lower than the value from static compression, and its uncertainty is lower by a factor of 3. The elastic constants of fluorite increase almost linearly with pressure over the whole investigated pressure range. However, at P ≥ 9 GPa, C 11 and C 12 show a subtle structure in their pressure dependence while C 44 does not. The behavior of the elastic constants of fluorite in the 9–9.3 GPa pressure range is probably affected by the onset of a high-pressure structural transition to a lower symmetry phase (α-PbCl2 type). A single-crystal Raman scattering experiment performed in parallel to the Brillouin measurements shows the appearance of new features at 8.7 GPa. The new features are continuously observed to 49.2 GPa, confirming that the orthorhombic high-pressure phase is stable along the whole investigated pressure range, in agreement with a previous X-ray diffraction study of CaF2 to 45 GPa. The high-pressure elasticity data in combination with room-pressure values from previous studies allowed us to determine an independent room-temperature compression curve of fluorite. The new compression curve yields a maximum discrepancy of 0.05 GPa at 9.5 GPa with respect to that derived from static compression by Angel (1993). This comparison suggests that the accuracy of the fluorite pressure scale is better than 1% over the 0–9 GPa pressure range. Received: 10 July 2001 / Accepted: 7 March 2002  相似文献   

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