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1.
The low-temperature heat capacity (C p ) of KAlSi3O8 with a hollandite structure was measured over the range of 5–303 K with a physical properties measurement system. The standard entropy of KAlSi3O8 hollandite is 166.2±0.2 J mol−1 K−1, including an 18.7 J mol−1 K−1 contribution from the configurational entropy due to disorder of Al and Si in the octahedral sites. The entropy of K2Si4O9 with a wadeite structure (Si-wadeite) was also estimated to facilitate calculation of phase equilibria in the system K2O–Al2O3–SiO2. The calculated phase equilibria obtained using Perple_x are in general agreement with experimental studies. Calculated phase relations in the system K2O–Al2O3–SiO2 confirm a substantial stability field for kyanite–stishovite/coesite–Si-wadeite intervening between KAlSi3O8 hollandite and sanidine. The upper stability of kyanite is bounded by the reaction kyanite (Al2SiO5) = corundum (Al2O3) + stishovite (SiO2), which is located at 13–14 GPa for 1,100–1,400 K. The entropy and enthalpy of formation for K-cymrite (KAlSi3O8·H2O) were modified to better fit global best-fit compilations of thermodynamic data and experimental studies. Thermodynamic calculations were undertaken on the reaction of K-cymrite to KAlSi3O8 hollandite + H2O, which is located at 8.3–10.0 GPa for the temperature range 800–1,600 K, well inside the stability field of stishovite. The reaction of muscovite to KAlSi3O8 hollandite + corundum + H2O is placed at 10.0–10.6 GPa for the temperature range 900–1,500 K, in reasonable agreement with some but not all experiments on this reaction.  相似文献   

2.
Phase relations in the system KAlSi3O8-NaAlSi 3O8 have been examined at pressures of 5–23 GPa and temperatures of 700–1200° C. KAlSi3O8 sanidine first dissociates into a mixture of wadeite-type K2Si4O9, kyanite and coesite at 6–7 GPa, which further recombines into KAlSi3O8 hollandite at 9–10 GPa. In contrast, NaAlSi3O8 hollandite is not stable at 800–1200° C near 23 GPa, where the mixture of jadeite plus stishovite directly changes into the assemblage of calcium ferrite-type NaAlSiO4 plus stishovite. Phase relations in the system KAlSi3O8-NaAlSi3O8 at 1000° C show that NaAlSi3O8 component gradually dissolves into hollandite with increasing pressure. The maximum solubility of NaAlSi3O8 in hollandite at 1000° C was about 40 mol% at 22.5 GPa, above which it decreases with pressure. Unit cell volume of the hollandite solid solution decreases with increasing NaAlSi3O8 component. The hollandite solid solution in this system may be an important candidate as a host mineral of K and Na in the uppermost lower mantle  相似文献   

3.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K).  相似文献   

4.
The 1-bar structure and properties of the high-pressure SiO2 polymorph coesite have been simulated by lattice and molecular dynamics up to 1600 and 2100 K, respectively. In agreement with available experimental data, the monoclinic structure was found metastable (with respect to cristobalite or SiO2 liquid) up to the highest temperatures investigated. Thermal expansion of coesite is small because of restricted rotations of SiO4 tetrahedra. Above about 1000 K, the structure of coesite becomes dynamically disordered and similar to those reported for the -phases of quartz and cristobalite. Disorder sets smoothly, however, in contrast to its abrupt onset in quartz and cristobalite, which have – transitions. The radial distribution functions for all bond distances indicate that order then prevails only for the nearest neighbors whereas the angle distributions widen markedly so that the monoclinic form of coesite with an Si–O–Si angle of 180° is only a time-averaged structure.  相似文献   

5.
The oxygen isotope compositions of coesite, sanidine, kyanite, clinopyroxene and garnet were measured in an ultra-high pressure-temperature grospydite from the Roberts Victor kimberlite, South Africa. The 18O values (per mil v. SMOW) of each phase and (1 ) are as follows: coesite, 8.62 (0.31); sanidine, 8.31 (0.02); kyanite, 7.98 (0.08); pyroxene, 7.63 (0.11); garnet, 7.53 (0.03). In situ analyses of the coesite with the laser extraction system are 18O=9.35 (0.08), n=4, demonstrating that the coesite is homogeneous. The coesite has partially inverted to polycrystalline quartz and the pyroxene is extensively altered during uplift. The larger scatter for the mineral separate coesite and pyroxene data may be due to partial reequilibration between the decompression-related breakdown products of these two phases. The anomalously high 18O value of the grospydite (18Owholerock=7.7) is consistent with altered oceanic crust as a source rock. Temperature estimates from a linear regression of all the data to three different published calibrations correspond to an equilibrium temperature of 1310±80°C. The calculated isotopic pressure effect is to lower these estimates by about 40°C at 40 kb. The estimated temperature based on Al–Si disorder in sanidine is 1200±100°C and that from Fe–Mg exchange thermometry between garnet and clinopyroxene is 1100±50°C. Given the large errors associated with thermometry at such high temperatures, it is concluded that the xenolith equilibrated that 1200±100°C. Pressure estimates are 45±5 kb, based on dilution of the univariant equilibria albite = jadeite + coesite and 2 kyanite + 3 diopside = grossular + pyrope + 2coesite. Zoning in the outer 20 m of the feldspar from Ab0.8 to Ab16 indicates rapid decompression to 25 kb or less. The isotopic temperature estimates are the highest ever obtained and combined with the high degree of Al–Si disorder in sanidine require rapid cooling from ultra-high temperatures. It is inferred that the xenolith was sampled at the time of equilibration, providing a point on the upper Cretaceous geotherm in the mantle below South Africa.  相似文献   

6.
The behaviour of synthetic Mg-ferrite (MgFe2O4) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K0=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by a0+a1*(T–298)+a2/(T–298)2, where a0=9.1(1) 10–6 K–1, a1=4.9(2) 10–9 K–2 and a2= 5.1(5) 10–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol–1 and =–17.6(± 1.2) kJ mol–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe2O4, which shows that the high-pressure transition from spinel to orthorombic CaMn2O4-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe2O3.  相似文献   

7.
The structure of CaGe2O5 between room temperature and 923 K has been determined by X-ray powder diffraction. A continuous phase transition from triclinic C1¯ to monoclinic C2/c symmetry at Tc=714±3 K is observed. The transition is accompanied by a weak heat capacity anomaly. This anomaly and the strain analysis based on the measured lattice parameters indicate a classical second-order phase transition. The order parameter, as measured by the strain component e23, is associated with the displacement of the Ca cation. Electronic structure optimization by density functional methods is used to verify the centric space group of the low-temperature structure of CaGe2O5.  相似文献   

8.
In situ X-ray diffraction study on KAlSi3O8 has been performed using the cubic type high pressure apparatus, MAX90, combined with synchrotron radiation. We determined the phase relations of sanidine, the wadeite-type K2Si4O9+kyanite (Al2SiO5)+coesite (SiO2) assemblage, and hollandite-type KAlSi3O8, including melting temperatures of potassic phases, up to 11 GPa. Our data on subsolidus phase boundaries are close to the recent data of Yagi and Akaogi (1991). Melting relations of sanidine are consistent with the low pressure data of Lindsley (1966). The breakdown of sanidine into three phases reduces melting temperature, and wadeite-type K2Si4O9 melts first around 1500° C in three phase coexisting region. Melting point of hollandite-type KAlSi3O8 is between 1700° C and 1800° C at 11 GPa. If these potassic phases host potassium in the earth's mantle, the true mantle solidus temperature will be much lower than the reported dry solidus temperature of peridotite.  相似文献   

9.
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   

10.
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   

11.
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   

12.
A dense (~3.34 g cm–3) garnet–sillimanite-rich metamorphic rock from the suevite breccia of the Ries impact crater was studied by scanning-electron microscopy and Raman microprobe spectroscopy. In the strongly shocked rock clast kyanite was formed from sillimanite under momentary high pressures of natural shock waves. Kyanite aggregates were found as thin (~0.3–2.0 m) seams along grain boundaries between, and fractures within, sillimanite grains. Within these seams kyanite c-axes are oriented perpendicular to original grain boundaries and fractures. In addition, larger (up to 10 m) isolated kyanite grains were rarely found within host sillimanite. Filamentary kyanite aggregates and isolated crystals typically show shrinkage cracks due to volume decrease (~10%). Locally, broad interstices between sillimanite crystals are filled with aluminosilicate glass containing a high volume fraction of sub-micrometer-sized euhedral crystals. The silica-rich glass suggests incongruent melting of sillimanite at local post-shock temperatures significantly higher than 1,300°C. The edges of adjacent sillimanite grains are thermally and chemically altered. The local generation of temperature spikes is attributed to strong shock wave interactions due to very high shock impedance contrasts.  相似文献   

13.
The mineral ussingite, Na2AlSi3O8(OH), an interrupted tectosilicate, has strong hydrogen bonding between OH and the other nonbridging oxygen atom in the structure. Infrared spectra contain a strongly polarized, very broad OH-stretching band with an ill-defined maximum between 1500 and 1800 cm–1, and a possible OH librational bending mode at 1295 cm–1. The IR spectra confirm the orientation of the OH vector within the triclinic unit cell as determined from X-ray refinement (Rossi et al. 1974). There are three distinct bands in the 1H NMR spectrum of ussingite: a predominant band at 13.5 ppm (TMS) representing 90% of the structural hydrogen, a second band at 15.9 ppm corresponding to 8% of the protons, and a third band at 11.0 ppm accounting for the remaining 2% of structural hydrogen. From the correlation between hydrogen bond length and 1H NMR chemical shift (Sternberg and Brunner 1994), the predominant hydrogen bond length (H...O) was calculated to be 1.49 Å, in comparison to the hydrogen bond length determined from X-ray refinement (1.54 Å). The population of protons at 15.9 ppm is consistent with 5–8% Al–Si disorder. Although the ussingite crystal structure and composition are similar to those of low albite, the bonding environment of OH in low albite and other feldspars, as characterized through IR and 1H NMR, is fundamentally different from the strong hydrogen bonding found in ussingite.  相似文献   

14.
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   

15.
The structural behavior of -eucryptite (LiAlSiO4) has been investigated using infrared (IR) spectroscopy over a temperature range of 20 to 900 K and FT-Raman spectroscopy at room temperature. IR reflectance measurements show that -eucryptite possesses high reflectivity in the far-IR region, as is consistent with its reported superionic conductivity along the c-axis. On heating, the Li-related IR bands near 246 and 300 cm–1 (with A2 symmetry) broadened and weakened dramatically, presumably as a result of Li+ positional disordering along the structural channels parallel to c. The disordering process appears to induce a framework distortion, as is evidenced by the broadening of some vibrations of Si(Al)–O with increasing temperature. A change in slope in the temperature dependence of the phonon frequency near 300 cm–1 and the linewidth of the 760 cm–1 band at 715 K indicates that Li becomes completely disordered above this temperature. In addition, the temperature dependence of the linewidth for the 760 cm–1 band exhibits an additional change in slope at 780 K, implying the existence of an intermediate state within this temperature range. The detailed structure of this intermediate phase, however, needs further study. Our IR data provide no indication of structural changes between room temperature and 20 K.  相似文献   

16.
Batisivite has been found as an accessory mineral in the Cr-V-bearing quartz-diopside metamorphic rocks of the Slyudyanka Complex in the southern Baikal region, Russia. A new mineral was named after the major cations in its ideal formula (Ba, Ti, Si, V). Associated minerals are quartz, Cr-V-bearing diopside and tremolite; calcite; schreyerite; berdesinskiite; ankangite; V-bearing titanite; minerals of the chromite-coulsonite, eskolaite-karelianite, dravite-vanadiumdravite, and chernykhite-roscoelite series; uraninite; Cr-bearing goldmanite; albite; barite; zircon; and unnamed U-Ti-V-Cr phases. Batisivite occurs as anhedral grains up to 0.15–0.20 mm in size, without visible cleavage and parting. The new mineral is brittle, with conchoidal fracture. Observed by the naked eye, the mineral is black and opaque, with a black streak and resinous luster. Batisivite is white in reflected light. The microhardness (VHN) is 1220–1470 kg/mm2 (load is 30 g), the mean value is 1330 kg/mm2. The Mohs hardness is near 7. The calculated density is 4.62 g/cm3. The new mineral is weakly anisotropic and bireflected. The measured values of reflectance are as follows (λ, nm—R max ′ /R min ′ ): 440—17.5/17.0; 460—17.3/16.7; 480—17.1/16.5; 500—17.2/16.6; 520—17.3/16.7; 540—17.4/16.8; 560—17.5/16.8; 580—17.6/16.9; 600—17.7/17.1; 620—17.7/17.1; 640—17.8/17.1; 660—17.9/17.2; 680—18.0/17.3; 700—18.1/17.4. Batisivite is triclinic, space group P \(\overline 1\); the unit-cell dimensions are: a = 7.521(1) Å, b = 7.643(1) Å, c = 9.572(1) Å, α = 110.20°(1), β = 103.34°(1), γ = 98.28°(1), V = 487.14(7) Å3, Z = 1. The strongest reflections in the X-ray powder diffraction pattern [d, Å (I, %)(hkl)] are: 3.09(8)(12\(\overline 2\)); 2.84, 2.85(10)(021, 120); 2.64(8)(21\(\overline 3\)); 2.12(8)(31\(\overline 3\)); 1.785(8)(32\(\overline 4\)), 1.581(10)(24\(\overline 2\)); 1.432, 1.433(10)(322, 124). The chemical composition (electron microprobe, average of 237 point analyses, wt %) is: 0.26 Nb2O5, 6.16 SiO2, 31.76 TiO2, 1.81 Al2O3, 8.20 VO2, 26.27 V2O3, 12.29 Cr2O3, 1.48 Fe2O3, 0.08 MgO, 11.42 BaO; the total is 99.73. The VO2/V2O3 ratio has been calculated. The simplified empirical formula is (V 4.8 3+ Cr2.2V 0.7 4+ Fe0.3)8.0(Ti5.4V 0.6 4+ )6.0[Ba(Si1.4Al0.5O0.9)]O28. An alternative to the title formula could be a variety (with the diorthogroup Si2O7) V8Ti6[Ba(Si2O7)]O22. Batisivite probably pertains to the V 8 3+ Ti 6 4+ [Ba(Si2O)]O28-Cr 8 3+ Ti 6 4+ [Ba(Si2O)]O28 solid solution series. The type material of batisivite has been deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.  相似文献   

17.
A pyroxene with composition LiNiSi2O6 was synthesized at T = 1,473 K and P = 2.0 GPa; the cell parameters at T = 298 K are a = 9.4169(6) Å, b = 8.4465(7) Å, c = 5.2464(3) Å, β = 110.534(6)°, V = 390.78(3) Å3. TEM examination of the LiNiSi2O6 pyroxene showed the presence of h + k odd reflections indicative of a primitive lattice, and of antiphase domains obtained by dark field imaging of the h + k odd reflections. A HT in situ investigation was performed by examining TEM selected area diffraction patterns collected at high temperature and synchrotron radiation powder diffraction. In HTTEM the LiNiSi2O6 was examined together with LiCrSi2O6 pyroxene. In LiCrSi2O6 the h + k odd critical reflections disappear at about 340 K; they are sharp up to the transition temperature and do not change their shape until they disappear. In LiNiSi2O6 the h + k odd reflections are present up to sample deterioration at 650 K. A high temperature synchrotron radiation powder diffraction investigation was performed on LiNiSi2O6 between 298 and 773 K. The analysis of critical reflections and of changes in cell parameters shows that the space group is P-centred up to the highest temperature. The comparative analysis of the thermal and spontaneous strain contributions in P21/c and C2/c pyroxenes indicates that the high temperature strain in P-LiNiSi2O6 is very similar to that due to thermal strain only in C2/c spodumene and that a spontaneous strain contribution related to pre-transition features is not apparent in LiNiSi2O6. A different high-temperature behaviour in LiNiSi2O6 with respect to other pyroxenes is suggested, possibly in relation with the presence of Jahn–Teller distortion of the M1 polyhedron centred by low-spin Ni3+.  相似文献   

18.
 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   

19.
Phase behaviors of kalsilite (KAlSiO4), leucite (KAlSi2O6) and sanidine (KAlSi3O8) at high pressures and temperatures have been reviewed. New experimental data for leucite composition were obtained in a diamond-anvil press coupled with laser heating. At about 1,000° C, the leucite composition breaks down into an assemblage of kalsilite +kyanite+K2Si4O9 (wadeite-type) in the range 60 to 120 kbar, of kalsilite+KAlSi3O8 (hollandite-type) in the range 120 to 150 kbar, and of KAlSi3O8 (hollandite-type) + KAlO2 (?) at 170 kbar or above. The suggestion that kalsilite is the most appropriate potassium silicate in the anhydrous upper mantle needs to be revised. It is suggested that the wadeite-type K2Si4O9 is the most appropriate host for potassium in the upper mantle at depths greater than about 150 km.  相似文献   

20.
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   

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