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1.
Simultaneous measurements of compressional and shear wave velocities, Vp and Vs, in acidic and basic igneous rocks and volcanic glasses, were made up to 900°C and at 10–20 kbar.The effects of pressure and temperature on Vp and Vs in glasses and glassy rocks change at about 600°C, presumably the glass transition temperature. These effects are directly related to the silica content in the samples. and for obsidian are negative at room temperature and 245°C, but are positive at 655°C. The velocity—pressure relations for obsidian display an obvious hysteresis phenomena. for basalt glass is slightly negative, but is positive for usual substances at room temperature, and for obsidian and glassy andesite are positive up to about 600°C but are negative above that temperature. However, for basalt glass as well as other crystalline rocks, and are negative at all temperatures. Glass once heated above the glass transition temperature Tg under pressure P1 retains the memory of pressure P1 after it is cooled down below Tg and while subjected to another pressure P2. An abrupt shift of the velocities correlating to pressure P2 occurs when the glass is again heated to Tg. Vp−T and Vs−T relations for obsidian, glassy andesite, and basalt glass clearly exhibit this pressure memory.  相似文献   

2.
The synthetic amphibole Na0.95(Li0.95Mg1.05)Mg5Si8O22(OH)2 was studied in situ at high-T, using IR OH-stretching spectroscopy and synchrotron X-ray powder diffraction. At room-T the sample has P21 /m symmetry, as shown by the FTIR spectrum. It shows in the OH region two well-defined and intense absorptions at 3,748 and 3,712 cm−1, respectively, and two minor bands at 3,667 and 3,687 cm−1. The main bands are assigned to the two independent O–H groups in the primitive structure. The two minor bands evidencing the presence of small amount of vacant A-site (A□0.05). With increasing T, these bands shift continuously and merge into a unique absorption at high temperature. A change as a function of increasing T is revealed by the evolution of the refined unit-cell parameters, whose trend shows a transition to C2/m at about 320–330°C. The spontaneous scalar strain, fitted with a tricritical 2–6 Landau potential, gives a T c of 325(10)°C (β parameter = 0.27). Comparison with the second-order P21 /m ⇔ C2/m phase transition at 255°C for synthetic amphibole ANa0.8B(Na0.8Mg1.2)CMg5Si8O22(OH)2 indicates that the substitution of Na with Li at the B-sites strongly affects the thermodynamic character and the T c of the phase transition. The comparison of LNMSH amphiboles with cummingtonitic ones shows that the high-T thermodynamic behaviour is affected by A-site occupancy.  相似文献   

3.
Diffusion coefficients (D) of hydrogen in fused silica capillaries (FSC) were determined between 296 and 523 K by Raman spectroscopy using CO2 as an internal standard. FSC capsules (3.25 × 10−4 m OD, 9.9 × 10−5 m ID, and 0.01 m long) containing CO2 and H2 were prepared and the initial relative concentrations of hydrogen in these capsules were derived from the Raman peak-height ratios between H2 (near 587 cm−1) and CO2 (near 1387 cm−1). The sample capsules were then heated at a fixed temperature (T) at one atmosphere to let H2 diffuse out of the capsule, and the changes of hydrogen concentration were monitored by Raman spectroscopy after quench. This process was repeated using different heating durations at 296 (room T), 323, 375, 430, 473, and 523 K; the same sample capsule was used repeatedly at each temperature. The values of D (in m2 s−1) in FSC were obtained by fitting the observed changes of hydrogen concentration in the FSC capsule to an equation based on Fick’s law. Our D values are in good agreement with the more recent of the two previously reported experimental data sets, and both can be represented by:
where R is the gas constant (8.3145 J/mol K), T in Kelvin, and errors at 1σ level. The slope corresponds to an activation energy of 44.59 ± 0.14 kJ/mol.The D in FSC determined at 296 K is about an order of magnitude higher than that in platinum at 723 K, indicating that FSC is a suitable membrane for hydrogen at temperature between 673 K and room temperature, and has a great potential for studying redox reactions at these temperatures, especially for systems containing organic material and/or sulphur.  相似文献   

4.
A simple mathematical relation among the dip of isograd surface (θ), dip of isotherm surface (α), temperature gradient (Tg), pressure gradient (Pg) and δT/gdP of reaction is given by:
Full-size image (1K)
Pg is taken to be constant at 0.3 kb/km. Four major theoretical models for shapes and orientations of isograds are formulated on the basis of the parameters α, Tg and δT/δP. This offers a rational basis for studying the geometry of isograds, normal/reverse metamorphism and determination of temperature gradient. Two examples have been studied in the light of these models; in one case the domed shape of the isograd is best explained by a downwardly directed Tg; in the other case, reverse metamorphism is best explained as the result of a horizontal Tg of 18°C/km.  相似文献   

5.
Lattice parameters, and intensities of selected X-ray reflexions, have been measured as a function of temperature for natural leucite, to characterise the phase transformation behaviour. At low temperatures leucite has a large ferroelastic distortion, but the temperature evolution of lattice parameters cannot be explained in terms of a purely ferroelastic phase transition; in particular, the considerable change in volume with temperature implies an additional transition mechanism, which we correlate with off-centring of K-ions in the low-temperature phase, and a collapse of the 111 structural channels. The transition behavior can therefore be rationalised in terms of two competing mechanisms: (I) Ferroelastic (consistent with the change m3m 4/mmm); (II) Volume-changing (consistent with m3m 4/m). Coupling of the two order parameters QI, and QII gives rise to the intermediate 4/mmm tetragonal phase.Our results confirm the existence of an I4 1/aI4 1/acd transition, but the non-disappearance of the 200 reflexion at high temperatures implies that the expected transition from I41/acd to Ia3d (cubic) symmetry does not occur. We attribute this to a residual strain field conjugated to the order parameter, due to defects (with possible Al/Si order). Nevertheless, within our experimental resolution, the lattice becomes metrically cubic at 665° C.  相似文献   

6.
The polarized single-crystal Raman spectrum of synthetic fayalite, Fe2SiO4, was recorded between 5 and 773 K in order to investigate its lattice dynamic behavior. A broad absorption envelope is observed at wavenumbers between 800 and 960 cm–1 and it contains two intense bands at 816 and 840 cm–1 at 293 K in the (cc) spectrum. The integral area of the envelope decreases upon cooling from 293 K and reaches a minimum around 55 K. It then increases again with a further decrease in temperature down to 5 K. It is proposed that the envelope in the (cc) spectra consists of seven different modes, some of which are symmetry-forbidden, that arise from combination scattering of nonsymmetric internal SiO4-stretching modes of Big symmetry (i = 1, 2, 3) and low-energy excitations. The individual modes can be observed under different polarizations and agree in number and wavenumber with those obtained by fitting the broad envelope with Lorentzians. An analysis of the Raman spectrum as a function of temperature, using the known magnetic properties of fayalite, allows the assignment of the low-energy excitations to short-range magnetic interactions. Modulation of the Fe2+(1)–Fe2+(2) exchange energy leads to phonon-magnetic excitation coupling and the main role in the Fe2+(1)–Fe2+(2) magnetic interaction occurs via superexchange through the oxygens. The magnetic excitations are not magnons in the usual sense, that is as quasiparticles having a long wavelength in an ordered system. The degree of observed broadening of the SiO4-stretching modes is consonant with a Fe2+(1)–Fe2+(2) exchange energy of 4.7 cm–1 presented by Schmidt et al. (1992). At temperatures above 300 K the line width of the mode at 840 cm–1 decreases slightly, whereas those of low energy lattice modes increase. This suggests that a decrease in mode broadening due to weakened magnetic interactions compensates any thermally related broadening. Complete Fe2+ spin disorder may not be reached until at least 530 K. Results from this study show that estimates of third-law entropies for silicates using simple crystal-chemical considerations that do not account for magnetic properties cannot give accurate values for many transition-metal-containing phases.  相似文献   

7.
The enthalpy of calcite has been measured directly between 973 K and 1325 K by transposed-temperature- drop calorimetry. The excess enthalpy has been analysed in terms of Landau theory for this tricritical phase transition. The zero-point enthalpy and entropy allow estimates of the parameters a and C in the Landau expansion for free energy which expresses excess free energy G as a function of the order parameter Q and temperature T: G 1/2a(T 2c–T)Q 2+1/6CQ 6 with a=24 J·K·mol-1, C = 30 kJ·mol– T c = 1260 ±5 K. The entropy of disorder below the transition has been formulated as a function of temperature allowing the calculation of the calcite/aragonite phase boundary when taking this extra entropy into account. There is remarkable agreement between the calculated equilibrium curve and previous experimental observations. The Landau theory predicts behaviour which fully accounts for the change in slope of the calcite/aragonite phase boundary, which is thus wholly due to the R¯3c –R¯3m transition in calcite.  相似文献   

8.
Neutron powder diffraction measurements of the temperature dependence of superlattice reflections in calcite have shown that there is a continuous phase transition at 1260 K. The change in space group symmetry and the halving of the unit cell size on heating indicate that this transition is an orientational order/disorder transition. The intensities of the superlattice reflections show that the temperature dependence of the order parameter, Q, is of the form (T c –T), where is 0.25, indicating that the transition is tricritical. The transition is accompanied by a large contraction along the c axis on cooling, defining a spontaneous strain e3 which is related to the order parameter (and hence temperature) via e3 Q 2. No evidence for critical lowering of the value of was found. These measurements confirm that, apart from the detailed critical behaviour, the phase transition in calcite is similar to that observed in NaNO3.  相似文献   

9.
 High-pressure and high-temperature Raman spectra of CaGeO3 tetragonal garnet have been collected to 11.5 GPa and 1225 K, respectively, in order to investigate possible intrinsic anharmonic behaviour in this phase. The Raman peak positions were observed to vary linearly with pressure and temperature within the ranges studied, with the higher-energy peaks showing larger P- and T-induced shifts than the low energy modes. The observed T-induced shifts are similar to those reported for grossular and andradite, while the observed P-induced shifts are generally larger than those of aluminosilicate and MgSiO3 majorite garnets (Gillet et al. 1992; Rauch et al. 1996) due to the larger bulk modulus of CaGeO3 garnet. The observed mode shifts of CaGeO3 garnet were used to determine the isothermal and isobaric mode Grüneisen parameters for this phase. These parameters are similar in value to those reported previously for grossular and andradite (Gillet et al. 1992). The calculated intrinsic anharmonic parameters, a i , for CaGeO3 garnet were determined to be nonzero, indicating significant anharmonic behaviour for this phase. These values, which range from −3.8 × 10−5 K−1 to −1.3 × 10−5 K−1, are also similar to those reported for andradite and grossular, but smaller than those determined for pyrope (Gillet et al. 1992). Hence, we expect MgSiO3 majorite to show greater anharmonicity than the germanate analogue studied by us. The anharmonic parameters determined for CaGeO3 tetragonal garnet may now be introduced into quasiharmonic vibrational heat capacity models to account for the observed anharmonic behaviour. Received: 21 April 1999 / Revised, accepted: 11 September 1999  相似文献   

10.
The temperature dependence (at ambient pressure) of the Raman spectra of both the quartz- and rutile-types of GeO2 has been studied from 109 to 874?K. All spectra were corrected for the effects of temperature and are presented in their reduced form to allow a direct comparison of intensities at all temperatures. In the quartz-type GeO2, the Raman bands above 400?cm?1 exhibited relatively larger temperature dependences and at least four of the bands in this region vary nonlinearly with increasing temperature. Deconvolution of the most intense Raman band at 700?cm?1 in the rutile-type GeO2 revealed the presence of a previously unreported band at 684?cm?1 at 298?K which may arise from splitting of the A1g mode. A nonlinear temperature dependence was observed for all the Raman bands above 600?cm?1 in the rutile-type GeO2 with the new band at 684?cm?1 exhibiting the largest curvature. In common with previous studies of rutile-type oxides, the B1g mode at 171?cm?1 showed anomalous behaviour by increasing linearly in frequency with increasing temperature. In a separate experiment, the oxidation of metallic germanium in air demonstrated that the quartz-type GeO2 is the preferred form of germanium oxide at temperatures above 745?K at atmospheric pressure. Thermodynamic calculations predict that the rutile-form of GeO2 should be the stable species under these conditions. This suggests that atmospheric gases may have a marked effect on the kinetics and stability of the quartz and rutile forms of GeO2.  相似文献   

11.
The infrared reflectivity spectra of two natural cassiterite single crystals from Portugal and Vietnam have been studied and analysed in the frequency range of 15–4000 cm–1 at room temperature. The optical mode parameters are deduced by simulation of the experimental spectra using the factorised form of the dielectric function. The difference with synthetic SnO2 spectra is a dip near 500 cm–1 understood as the activation of an infrared forbidden E g mode due to the amount of Fe3+ and Ti4+ impurities. Another result of this work is the derivation of the correct values of the static dielectric constant of cassiterite.  相似文献   

12.
 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   

13.
Seismic velocities under confining pressures to 10 kbar have been measured for rocks of the Ivrea—Verbano and Strona—Ceneri Zones of northern Italy, a metamorphic complex thought to represent a cross-section of the continental crust and crust—mantle boundary. Laboratory-determined compressional wave velocities for schists and gneisses of the amphibolite facies found in the upper levels of the section (having an average density of 2.74 g/cm3) average 6.45 km/sec at pressures between 6 and 10 kbar. These increase with depth to values greater than 7.1 km/sec for amphibolites and rocks of the amphibolite—granulite facies transition and to 7.5 km/sec. (average density 3.06 g/cm3) in intermediate and mafic granulite facies rocks near the base of the section. Compressional wave velocities then abruptly increase to 8.5 km/sec in ultramafic complexes near the Insubric Line. Regional geophysical surveys show that Pg is 6.0 km/sec (density of 2.7 g/cm3), P* is 7.2–7.4 km/sec (density of 3.1 g/cm3) and Pn is 8.1 km/sec, values which are in agreement with the laboratory data when effects of temperature are taken into consideration. Estimated thicknesses of exposed rock units are in reasonable agreement with thicknesses determined for crustal layers in seismic refraction experiments. The agreement between the regional crustal structure and the laboratory-determined values of velocity and density provides strong evidence for the hypothesis that the rocks of this metamorphic complex represent a cross-section of the continental crust of the Po Basin.Using the Ivrea—Verbano and Strona—Ceneri sequence as a model of the continental crust, the crust of northern Italy is shown to consist of a thick series of metamorphic rocks with greenschist facies rocks occupying the uppermost levels. These grade downward into amphibolite facies gneisses and schists with occasional granitic intrusives. The Conrad discontinuity is marked by a change from silicic and intermediate amphibolite facies gneisses to intermediate and mafic granulite facies rocks in which hydrous minerals diminish in abundance and thus represents a distinct transition in terms of both composition and metamorphic grade. The lower crust is dominated by a heterogeneous series of mafic and metapelitic rocks in the granulite facies. Importantly, metasedimentary rocks of intermediate silica content found in the complex can have compressional wave velocities equivalent to velocities in mafic rocks suggesting that the lower continental crust everywhere is not necessarily mafic in composition. Ultramafic complexes near the Insubric Line may represent the upper mantle of the continent and their setting suggests that the continental crust-upper mantle boundary is sharp and is not isochemical.  相似文献   

14.
We have obtained high quality Raman spectra for two H/D isotopically substituted hydrous aluminosilicate glasses with compositions along the NaAlSi3O8-SiO2 join. Consistent with the results of previous studies, the isotope shift for the band near 900 cm–1, whose intensity grows with increasing water content, is extremely small: v h /v d = 1.004 ± 0.004. The lack of a definite H/D isotope shift for this band does not, however, preclude its association with a vibration of a hydrous species in the glass, because of likely strong coupling between different vibrational modes of hydrated framework species. The 900 cm–1 band could well be due to a T — OH (T = Si, Al) stretching or bending vibration in the hydrous glass, as required by the presence of a combination band near 4500 cm–1 in near-infrared spectra.  相似文献   

15.
Kojitani  H.  Nishimura  K.  Kubo  A.  Sakashita  M.  Aoki  K.  Akaogi  M. 《Physics and Chemistry of Minerals》2003,30(7):409-415
Raman spectroscopy of calcium ferrite type MgAl2O4 and CaAl2O4 and heat capacity measurement of CaAl2O4 calcium ferrite were performed. The heat-capacity of CaAl2O4 calcium ferrite measured by a differential scanning calorimeter (DSC) was represented as CP(T)=190.6–1.116 × 107T–2 + 1.491 × 109T–3 above 250 K (T in K). The obtained Raman spectra were applied to lattice dynamics calculation of heat capacity using the Kieffer model. The calculated heat capacity for CaAl2O4 calcium ferrite showed good agreement with that by the DSC measurement. A Kieffer model calculation for MgAl2O4 calcium ferrite similar to that for CaAl2O4 calcium ferrite was made to estimate the heat capacity of the former. The heat capacity of MgAl2O4 calcium ferrite was represented as CP(T)=223.4–1352T –0.5 – 4.181 × 106T –2 + 4.300 × 108T –3 above 250 K. The calculation also gave approximated vibrational entropies at 298 K of calcium ferrite type MgAl2O4 and CaAl2O4 as 97.6 and 114.9 J mol–1 K–1, respectively.  相似文献   

16.
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   

17.
Natural Fe2+, Fe3+-bearing spinel solid solutions from the spinel s.s.-hercynite and gahnite-hercynite series were analyzed and studied by electronic absorption spectroscopy in the spectral range 30000–3500 cm–1 in the temperature and pressure ranges 77 TK 600 and 10–4 PGPa 11.0. Two crystals were light-violet in color (type I) and six green or bluish-green (type II). The spectra of both types of spinels are dominated by an UV-absorption edge near 28000 to 24000 cm–1, depending on the iron contents, and a very intense band system in the NIR centered around 5000 cm–1, which is caused by spin-allowed dd-transition of tetrahedral Fe2+, derived from 5 E5 T2. The strong band is in all spinels studied, split into four sub-bands, which can only be observed in very thin platelets. Between the UV-edge and the high-energy wing of the NIR-band there occur a number of very weak bands in type I spinels while the green type II spinels show some of these with significantly enhanced intensity. The intensity of the very weak bands is nearly independent from temperature. Such bands are attributed to spin-forbidden electronic transitions of IVFe2+. Temperature and pressure dependence of the intensity enhanced bands of spinels type II indicate that they are caused by IVFe2+ and VIFe3+. They are attributed to spin-forbidden transitions 6A1g4A1g, 4Eg, 4T2g and 4T1g of VIFe3+, the two latter being strongly intensified by exchange-coupling interaction with adjacent IVFe2+. The pressure dependence of IVFe2+ dd-band system in the NIR caused by spin-allowed 5 E5 T2 transition noticeably differs from that of octahedral Fe2+, an effect which is attributed to a dynamic Jahn-Teller effect of IVFe2+ in the spinel structure.
Monika Koch-MüllerEmail: Phone: +49-331-288-1492/1402Fax: +49-331-288-1492/1402
  相似文献   

18.
Crystal field spectra have been obtained from K2Co2(SO4)3 at a number of temperatures from 20 K to room temperature. The transition to the 4 T 1g(P) excited state is found to be split at all temperatures owing to the trigonal distortion of the Co site. Below the P213-P212121 phase transition temperature an excess splitting is observed owing to the additional distortion of the site in the orthorhombic phase. This excess distortion is found to be a linear function of temperature with no first order step at T c. Thus on a local scale the transition appears to be second order. The trigonal splitting increases with increasing temperature above Tc; this is not expected from the Speer-Salje model of the transition mechanism, which predicted decreasing distortion of the oxygen octahedra with increasing temperature. We propose that the apparent increase of asymmetry is due to the off centring of the Co atom in the high temperature phase in a more regular environment.  相似文献   

19.
Majorite of bulk composition Mg0.86Fe0.15SiO3 was synthesized at 19 GPa and 1900 °C at an oxygen fugacity close to the Re/ReO2 buffer. Optical absorption spectra of polycrystalline samples were measured from 4000 to 25000cm?1. The following features were observed: (1) Three bands at 4554, 6005 and 8093 cm?1 due to the 5Eg → 5T2g transition of Fe2+ in a distorted dodecahedral site. (2) A band at 9340 cm?1 due to the transition 5T2g → 5Eg of octahedral Fe2+. (3) A band at 22784 cm?1 resulting from Fe3+, probably in an octahedral site (6A1g → 4A1g, 4Eg). (4) A very intense system of Fe2+ → Fe3+ intervalence charge transfer bands which can be modelled by two Gaussian components centered at 16542 and 20128 cm?1. The existence of two components in the charge transfer spectrum could be related to the fact that the tetragonal majorite structure may contain Fe3+ in two different octahedral sites. The crystal field splitting Δ of Fe2+ in dodecahedral coordination is 5717 cm?1. If a splitting of the ground state in the order of 1000 cm?1 is assumed, this yields a crystal field stabilization energy (CFSE) of 3930 cm?1, comparable to the CFSE of Fe2+ in pyrope-rich garnet. However, the splitting of 5T2g is significantly higher than in pyrope. This would be consistent with Fe2+ preferentially occupying the more distorted one of the two dodecahedral sites in the majorite structure. For octahedral Fe2+, Δ= 9340 cm?1 and CFSE=3736 cm?1, assuming negligible splitting of the ground state.  相似文献   

20.
Polarized single crystal Raman spectra of the langbeinite K2Cd2(SO4)3 were recorded for different polarisations. With a view to understanding the phase transition mechanism, the lattice vibrational spectra (0–300 cm?1), as well as the SO4 symmetric stretching mode v 1 (1,022 cm?1), were recorded at different temperatures. No soft modes were observed. From the study of the temperature variation of the integrated intensity I 0 and band width Γ of the hard mode (1,022 cm?1), both SO4 libration and SO4 order/disorder models were ruled out as possible phase transition models. On the other hand, the model of Speer and Salje (paper I), involving the distortion of the polyhedra around Cd and K ions, explains the observed temperature behaviour of the Raman spectra very well. The consequences of a possible hypothetical high-temperature phase are discussed.  相似文献   

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