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1.
Using a conventional high-T furnace, the solid solutions between magnesiochromite and manganochromite, (Mg1−x Mn x )Cr2O4 with x = 0.00, 0.19, 0.44, 0.61, 0.77 and 1.00, were synthesized at 1,473 K for 48 h in open air. The ambient powder X-ray diffraction data suggest that the V–x relationship of the spinels does not show significant deviation from the Vegard’s law. In situ high-T powder X-ray diffraction measurements were taken up to 1,273 K at ambient pressure. For the investigated temperature range, the unit-cell parameters of the spinels increase smoothly with temperature increment, indicating no sign of cation redistribution between the tetrahedral and octahedral sites. The V–T data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (aT = a0 + a1 T + a2 T - 2 \alpha_{T} = a_{0} + a_{1} T + a_{2} T^{ - 2} ), which yielded insignificant a 2 values. The effect of the composition on a 0 is adequately described by the equation a 0 = [17.7(8) − 2.4(1) × x] 10−6 K−1, whereas that on a 1 by the equation a 1 = [8.6(9) + 2.1(11) × x] 10−9 K−2.  相似文献   

2.
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   

3.
The melting temperature of Fe–18 wt% Si alloy was determined up to 119 GPa based on a change of laser heating efficiency and the texture of the recovered samples in the laser-heated diamond anvil cell experiments. We have also investigated the subsolidus phase relations of Fe–18 wt% Si alloy by the in-situ X-ray diffraction method and confirmed that the bcc phase is stable at least up to 57 GPa and high temperature. The melting curve of the alloy was fitted by the Simon’s equation, P(GPa)/a = (T m(K)/T 0) c , with parameters, T 0 = 1,473 K, a = 3.5 ± 1.1 GPa, and c = 4.5 ± 0.4. The melting temperature of bcc Fe–18 wt% Si alloy is comparable with that of pure iron in the pressure range of this work. The melting temperature of Fe–18 wt% Si alloy is estimated to be 3,300–3,500 K at 135 GPa, and 4,000–4,200 K at around 330 GPa, which may provide the lower bound of the temperatures at the core–mantle boundary and the inner core–outer core boundary if the light element in the core is silicon.  相似文献   

4.
The high-pressure and temperature equation of state of majorite solid solution, Mj0.8Py0.2, was determined up to 23 GPa and 773 K with energy-dispersive synchrotron X-ray diffraction at high pressure and high temperature using the single- and double-stage configurations of the multianvil apparatuses, MAX80 and 90. The X-ray diffraction data of the majorite sample were analyzed using the WPPD (whole-powder-pattern decomposition) method to obtain the lattice parameters. A least-squares fitting using the third-order Birch-Murnaghan equation of state yields the isothermal bulk modulus, K T0  = 156 GPa, its pressure derivative, K′ = 4.4(±0.3), and temperature derivative (∂K T /∂T) P = −1.9(±0.3)× 10−2 GPa/K, assuming that the thermal expansion coefficient is similar to that of pyrope-almandine solid solution. Received: 5 October 1998 / Revised, accepted: 24 June 1999  相似文献   

5.
 The spinel solid solution was found to exist in the whole range between Fe3O4 and γ-Fe2SiO4 at over 10 GPa. The resistivity of Fe3− x Si x O4 (0.0<x<0.288) was measured in the temperature range of 80∼300 K by the AC impedance method. Electron hopping between Fe3+ and Fe2+ in the octahedral site of iron-rich phases gives a large electric conductivity at room temperature. The activation energy of the electron hopping becomes larger with increasing γ-Fe2SiO4 component. A nonlinear change in electric conductivity is not simply caused by the statistical probability of Fe3+–Fe2+ electron hopping with increasing the total Si content. This is probably because a large number of Si4+ ions occupies the octahedral site and the adjacent Fe2+ keeping the local electric neutrality around Si4+ makes a cluster, which generates a local deformation by Si substitution. The temperature dependence of the conductivity of solid solutions indicates the Verwey transition temperature, which decreases from 124(±2) K at x=0 (Fe3O4) to 102(±5) K at x=0.288, and the electric conductivity gap at the transition temperature decreases with Si4+ substitution. Received: 15 March 2000 / Accepted: 4 September 2000  相似文献   

6.
 The structural behavior of stuffed derivatives of quartz within the Li1− x Al1− x Si1+ x O4 system (0 ≤ x ≤ 1) has been studied in the temperature range 20 to 873 K using high-resolution powder synchrotron X-ray diffraction (XRD). Rietveld analysis reveals three distinct regimes whose boundaries are defined by an Al/Si order-disorder transition at x=∼0.3 and a β–α displacive transformation at x=∼0.65. Compounds that are topologically identical to β-quartz (0 ≤ x < ∼0.65) expand within the (0 0 1) plane and contract along c with increasing temperature; however, this thermal anisotropy is significantly higher for structures within the regime 0 ≤ x < ∼0.3 than for those with compositions ∼0.3 ≤ x < ∼0.65. We attribute this disparity to a tetrahedral tilting mechanism that occurs only in the ordered structures (0 ≤ x < ∼0.3). The phases with ∼0.65 ≤ x ≤ 1 adopt the α-quartz structure at room temperature, and they display positive thermal expansion along both a and c from 20 K to their α–β transition temperatures. This behavior arises mainly from a rotation of rigid Si(Al)-tetrahedra about the <100> axes. Landau analysis provides quantitative evidence that the charge-coupled substitution of Li+Al for Si in quartz dampens the α–β transition. With increasing Li+Al content, the low-temperature modifications exhibit a marked decrease in spontaneous strain; this behavior reflects a weakening of the first-order character of the transition. In addition, we observe a linear decrease in the α–β critical temperature from 846 K to near 0 K as the Li+Al content increases from x=0 to x=∼0.5. Received: 26 June 2000 / Accepted: 1 December 2000  相似文献   

7.
A suite of (Mn1-x Fe x )Nb2O6 (x=0, 0.05, 0.25, 0.50, 0.75, 1) columbite samples has been prepared by solid-state reaction from oxides. X-ray diffraction and spectroscopic investigations have been carried out in order to gain different perspectives on how the solid solution adapts at different length scales to cation mixing. X-ray powder diffraction and powder absorption IR spectroscopy data are presented. The powder diffraction data show that there is no significant excess volume of mixing on the Fe–Mn columbite join. All the unit-cell parameters decrease linearly as a function of increasing Fe content. Substitution of Fe2+ for the larger Mn2+ cation causes a decrease in the volume of the A polyhedron, which also becomes more regular with respect to both bond-length and edge-length distortion parameters. No significant variation of the B site has been observed. Wavenumber shifts of the IR peaks nearly all vary linearly with composition, consistent with linear variations of the lattice parameters. Line broadening has been quantified by autocorrelation analysis of the IR spectra. This is interpreted as suggesting that there is some element of local strain or positional disorder at the length scale of second or third nearest neighbours around sites occupied by Fe.  相似文献   

8.
Low-temperature isobaric heat capacities (C p ) of MgSiO3 ilmenite and perovskite were measured in the temperature range of 1.9–302.4 K with a thermal relaxation method using the Physical Properties Measurement System. The measured C p of perovskite was higher than that of ilmenite in the whole temperature range studied. From the measured C p , standard entropies at 298.15 K of MgSiO3 ilmenite and perovskite were determined to be 53.7 ± 0.4 and 57.9 ± 0.3 J/mol K, respectively. The positive entropy change (4.2 ± 0.5 J/mol K) of the ilmenite–perovskite transition in MgSiO3 is compatible with structural change across the transition in which coordination of Mg atoms is changed from sixfold to eightfold. Calculation of the ilmenite–perovskite transition boundary using the measured entropies and published enthalpy data gives an equilibrium transition boundary at about 20–23 GPa at 1,000–2,000 K with a Clapeyron slope of −2.4 ± 0.4 MPa/K at 1,600 K. The calculated boundary is almost consistent within the errors with those determined by high-pressure high-temperature in situ X-ray diffraction experiments.  相似文献   

9.
We used an in situ measurement method to investigate the phase transition of Fe2SiO4 polymorphs under high pressures and temperatures. A multi-anvil high-pressure apparatus combined with synchrotron X-ray radiation was used. The stability of each polymorph was identified by observing the X-ray diffraction data from the sample. In most experiments, the diffraction patterns were collected 10–30 min after reaching the desired pressure and temperature conditions. The transition boundary between the olivine and spinel phase at T = 1,000–1,500 K and P = 2–8 GPa was determined to occur at P (GPa) = 0.5 + 0.0034 × T (K). The transition pressure determined in this study was in general agreement with that observed in previous high-pressure experiments. However, the slope of the transition, dP/dT, determined in our study was significantly higher than that estimated by the previous study combined with the in situ X-ray method.  相似文献   

10.
The paraelectric to antiferroelectric phase transition in titanite at ～500 K involves a displacement of the titanium atom from the center of the [TiO6] octahedron in the paraelectric phase (A2/a) to an off-center position in the antiferroelectric (P2 1/a) phase. We have carried out a detailed single crystal high temperature x-ray diffraction study of the phase transition including structure refinements at 294, 350, 400, 430, 440, 450, 500, 600, and 700 K. The unit cell dimensions show a pronounced hysteresis effect in the 450–500 K range on heating and cooling during the first cycle along with a reduction of the transition temperature, T c from 495 ± 5 K on heating to 445 ± 5 K on cooling. The hysteresis effect disappears on further heating and the superstructure reflections show residual intensities above T c (445 K). An order parameter treatment of the phase transition is presented in terms of Landau theory and induced representation theory. The Ti-displacements parallel and antiparallel to a are taken as the primary order parameter η, which transforms as the Y 2 + representation. A coupling of Y 2 + with T 1 + results in the linear-quadratic coupling of the spontaneous strain components, ? ij with η. The Ti-displacements are coupled linearly to the Cadisplacements. Both sets of displacements predicted from induced representation theory are observed experimentally. The phase transition is initially driven by the soft mode at the zone boundary point Y 2 + ; near T c critical fluctuations set in and an order-disorder mechanism finally drives the phase transition, whereby parallel and antiparallel Ti-displacements related by [0, 1/2, 1/2] in adjacent domains are dynamically interchanged. Immediately above T c , the high temperature (A2/a) phase is a statistical average of small dynamic antiphase domains of the low temperature (P2 1/a) phase. Vacancies and defects pinning the domain boundaries may drastically alter the transition behavior and affect the domain mobility.  相似文献   

11.
The cell dimensions and crystal structures of the fluoroperovskite NaMgF3 (neighborite), synthesized by solid state methods, have been determined by powder neutron diffraction and Rietveld refinement over the temperature range 300–3.6 K using Pt metal as an internal standard for calibration of the neutron wavelength. These data show that Pbnm NaMgF3 does not undergo any phase transitions to structures of lower symmetry with decreasing temperature. The cell dimensions and atomic coordinates together with polyhedron volumes and distortion indices are given for Pbnm NaMgF3 at 25 K intervals from 300 to 3.6 K. Decreases in the a and c cell dimensions reach a saturation point at 50 K, whereas the b dimension becomes saturated at 150 K. The distortion of the structure of Pbnm NaMgF3 from the aristotype cubic structure is described in terms of the tilting of the MgF6 octahedra according to the tilt scheme a − a − c + . With decreasing temperature the antiphase tilt (a −) increases from 14.24° to 15.39°, whereas the in-phase tilt (c + ) remains effectively constant at ∼10.7°. Changes in the tilt angles are insufficient to cause changes in the coordination sphere of Na that might induce a low temperature phase transition. The structure of Pbnm NaMgF3 is also described in terms of normal mode analysis and displacements of the condensed normal modes are compared with those of Pbnm KCaF3.  相似文献   

12.
New in-situ high-temperature X-ray powder diffraction data on the normal-incommensurate phase transition in Co-åkermanite (Ca2CoSi2O7) are presented. Evidence for the phase transition is found in the abrupt change in the thermal expansivity of the c lattice parameter at 220° C. In addition, the c lattice parameter exhibits premonitory effects of the phase transition through the leveling out of the thermal expansivity at temperatures from 87 to 220° C. The c/a ratio for X2ZSi2O7 incommensurate melilites is shown to be constant for a wide variety of compositions. Correlation of the trends in mean atomic positions with c/a ratio and the sigmoidal variation in the c/a ratio for Ca2CoSi2O7 provide insight into the atomic displacements occurring in the melilite structure as a function of temperature. Three temperature regimes are discussed in detail (i.e. temperatures well above T c, temperatures just above T c, and temperatures below T c). The atomic displacements occurring in each temperature regime are correlated with the changes in anisotropy and orientation of the atomic displacement ellipsoids for each site, as well as spectroscopic evidence for the increasing number of Z- and T-site environments.  相似文献   

13.
In situ X-ray observations of the phase transition from ilmenite to perovskite structure in MnGeO3 were carried out in a Kawai-type high-pressure apparatus interfaced with synchrotron radiation. The phase boundary between the ilmenite and perovskite structures in the temperature range of 700–1,400°C was determined to be P (GPa) = 16.5(±0.6) − 0.0034(±0.0006)T (°C) based on Anderson’s gold pressure scale. The Clapeyron slope, dP/dT, determined in this study is consistent with that for the transition boundary between the ilmenite and the perovskite structure in MgSiO3.  相似文献   

14.
A high temperature single-crystal X-ray diffraction study of enstatite, Mg2Si2O6 was undertaken at 296, 900, 1200, 1360 and 1400 K. During the X-ray data collection at 1360 K (T0), orthoenstatite (Pbca) transformed to protoenstatite (Pbcn). The unit cell parameters measured at T0 are a=18.456(4), b=8.960(2) and c=5.270(1) Å for ortho and a=9.306(1), b=8.886(1) and c=5.360(1) Å for proto. The discontinuous increase in c and decrease in b due to the ortho to proto transformation are associated with the drastic unkinking of the silicate chains, whereas the abrupt increase in a results from the large expansion of the M2 — O distances along a coupled with the increase in the out-of-plane tilting of the silicate tetrahedra. Stacking faults form in ortho prior to the phase transition, as well as in proto between 1360 and 1400 K. With increasing temperature, the silicate B chain in ortho straightens faster than the A chain as the configurations of the SiA and SiB tetrahedra tend to become similar. At T0, the A and B chains with the O3-O3-O3 angles (O3 being the bridging oxygen atom) of 163.0° and 149.5° in ortho, respectively, attain an identical angle of 168.4° in proto. The configuration of the silicate chain in proto resembles that of the A chain in ortho. Rigid-body thermal vibration analysis suggests that between 1200 and 1400 K the largest, the second largest and the smallest thermal librational motions of the [SiO4] tetrahedra in both ortho and proto are approximately around a, c and b, respectively. Below 1200 K, the largest thermal librational amplitudes of the SiA and SiB tetrahedra in ortho are quite different, but become nearly equivalent at T0. In contrast to the results reported for all iron-bearing orthopyroxenes at high temperature, switching of the O3B atoms coordinated with the M2 cation occurs during the ortho to proto transformation, but not in ortho below T0. The ortho-proto transition does not affect the configuration of the M1 octahedron significantly, but results in a decrease of the mean M2 — O bond distance by 0.043 Å and a highly distorted M2 octahedron in proto.  相似文献   

15.
Thermal expansion has been measured by laboratory and synchrotron X-ray powder diffraction for end-member åkermanite (ak, Ca2MgSi2O7) and gehlenite (ge, Ca2Al2SiO7) in the range 20–1,500 K. In ak in the range 340–390 K, there is a negative linear thermal expansion in [001] direction. This is related to the phase transition from an incommensurate modulated structure (IC) to a normal one (N). The volumetric mean thermal expansion coefficients for ak and ge, obtained with a linear fit of the experimental data in the temperature range 298–1,400 K, are respectively 32.1×10–6 and 28.3×10–6 K–1 . The variation of the c/a ratio with temperature, due to different thermal expansion along the crystallographic axes, can be related to the different behaviour of the tetrahedral layers in the N and IC phases. Analysis of the variation of the superstructure peaks intensity across the phase transition confirms the tricritical behaviour of the IC/N transition in ak.  相似文献   

16.
 The order-disorder phase transitions in NaNO3 and CaCO3 are simulated by molecular dynamics. The simulations are based on the potentials calculated from the Gordon–Kim modified electron gas formalism extended to molecular ions. We successfully reproduced the transition temperature T c and the abnormally large c axis thermal expansion observed in experiment. The phase transitions in NaNO3 and CaCO3 were found to be initiated by ±60 and ±180° reorientation of the NO3 and CO3 ions about the c axis. The orientations of NO3 and CO3 ions are continuous with six preferred calcite-type orientations above the phase-transition temperature. Received: 30 January 2001 / Accepted: 11 May 2001  相似文献   

17.
In-situ X-ray powder diffraction measurements conducted under high pressure confirmed the existence of an unquenchable orthorhombic perovskite in ZnGeO3. ZnGeO3 ilmenite transformed into perovskite at 30.0 GPa and 1300±150 K in a laser-heated diamond anvil cell. After releasing the pressure, the lithium niobate phase was recovered as a quenched product. The perovskite was also obtained by recompression of the lithium niobate phase at room temperature under a lower pressure than the equilibrium phase boundary of the ilmenite–perovskite transition. Bulk moduli of ilmenite, lithium niobate, and perovskite phases were calculated on the basis of the refined X-ray diffraction data. The structural relations among these phases are considered in terms of the rotation of GeO6 octahedra. A slight rotation of the octahedra plays an important role for the transition from lithium niobate to perovskite at ambient temperature. On the other hand, high temperature is needed to rearrange GeO6 octahedra in the ilmenite–perovskite transition. The correlation of quenchability with rotation angle of GeO6 octahedra for other germanate perovskites is also discussed.  相似文献   

18.
The structural phase transition in titanite near 500 K (averaged symmetries A2/aP2 1/a) and a second anomaly around 900 K have been studied using infrared spectroscopy on single crystals aqnd powder samples, measurements of the dielectric properties and the specific heat. The same synthetic single crystal was used in all experiments.The phase transition near 500 K is associated with a break in the temperature evolution of phonon frequencies and absorption intensities. Some phonon signals decrease rapidly under further heating and their extrapolated intensities disappear at ca. 850 K. The most dominant temperature effect relates to Ti-O phonons with amplitudes along the crystallographic a axis. These phonons show large LO-To splitting and continue to soften under heating even at temperatures above the transitions point (ca. 500 K).  相似文献   

19.
The low-temperature isobaric heat capacities (C p) of β- and γ-Mg2SiO4 were measured at the range of 1.8–304.7 K with a thermal relaxation method using the Physical Property Measurement System. The obtained standard entropies (S°298) of β- and γ-Mg2SiO4 are 86.4 ± 0.4 and 82.7 ± 0.5 J/mol K, respectively. Enthalpies of transitions among α-, β- and γ-Mg2SiO4 were measured by high-temperature drop-solution calorimetry with gas-bubbling technique. The enthalpies of the α−β and β−γ transitions at 298 K (ΔH°298) in Mg2SiO4 are 27.2 ± 3.6 and 12.9 ± 3.3 kJ/mol, respectively. Calculated α−β and β−γ transition boundaries were generally consistent with those determined by high-pressure experiments within the errors. Combining the measured ΔH°298 and ΔS°298 with selected data of in situ X-ray diffraction experiments at high pressure, the ΔH°298 and ΔS°298 of the α−β and β−γ transitions were optimized. Calculation using the optimized data tightly constrained the α−β and β−γ transition boundaries in the P, T space. The slope of α−β transition boundary is 3.1 MPa/K at 13.4 GPa and 1,400 K, and that of β−γ boundary 5.2 MPa/K at 18.7 GPa and 1,600 K. The post-spinel transition boundary of γ-Mg2SiO4 to MgSiO3 perovskite plus MgO was also calculated, using the optimized data on γ-Mg2SiO4 and available enthalpy and entropy data on MgSiO3 perovskite and MgO. The calculated post-spinel boundary with a Clapeyron slope of −2.6 ± 0.2 MPa/K is located at pressure consistent with the 660 km discontinuity, considering the error of the thermodynamic data.  相似文献   

20.
The cell dimensions of the fluoroperovskite KMgF3 synthesized by solid state methods have been determined by powder neutron diffraction and Rietveld refinement over the temperature range 293–3.6 K using Pt metal as an internal standard for calibration of the neutron wavelength. These data demonstrate conclusively that cubic $ Pm\overline{3} m The cell dimensions of the fluoroperovskite KMgF3 synthesized by solid state methods have been determined by powder neutron diffraction and Rietveld refinement over the temperature range 293–3.6 K using Pt metal as an internal standard for calibration of the neutron wavelength. These data demonstrate conclusively that cubic KMgF3 does not undergo any phase transitions to structures of lower symmetry with decreasing temperature. Cell dimensions range from 3.9924(2) ? at 293 K to 3.9800(2) ? at 3.6 K, and are essentially constant within experimental error from 50 to 3.6 K. The thermal expansion data are described using a fourth order polynomial function.  相似文献   

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