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1.
The thermal phase transition of K2SO4 has been investigated by high temperature polarized light microscopy. K2SO4 undergoes a first-order transition at 587° C where the orthorhombic low temperature form (Pmcn) transforms into a hexagonal high temperature modification (P63/mmc). Prior to the beginning of the phase transition, K2SO4 shows an anomalous optical behavior. The crystal apparently becomes optically uniaxial twice at 338° and 425° C, respectively, and truly optically uniaxial at 587° C. The phase transition propagates through an intermediate temperature form, which is sandwiched between the low and the high temperature forms and moves in a definite direction, 〈130〉 (orthorhombic indices), in the vicinity of the phase transition. Passing through the phase transition point on cooling, dark belts crossing each other are observed which are a result of the transformation twins parallel to {110} and {130}.  相似文献   

2.
A natural Ca-rich pigeonite (En47Fs43Wo10), free of augite exsolution products, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2 1 /c (a=9.719(7) Å, b=8.947(9) Å, c=5.251(3) Å, β=108.49(5), V=433.0(6) Å3), was annealed up to 1000 °C to induce a phase transition from P2 1 /c to C2/c symmetry. Complete single-crystal X-ray diffraction data collections were carried out in situ at 650, 750, 850 and 950 °C after the crystal had reached equilibrium for the Fe–Mg intracrystalline exchange reaction at each temperature. The variation, with increasing temperature, of lattice parameters, of intensity of hkl reflections with h + k=2n + 1 (which vanish at high temperature) and of some geometrical parameters from structure refinement, showed that the displacive phase transition P2 1 /c?C2/c was continuous in character. This contrasts with the first-order character for the HT phase transition in pigeonite containing significantly less calcium.  相似文献   

3.
The phase transition of K2SO4 has been investigated by measurements of the dielectric constant and electrical conductivity, correlated with the structural point of view. Using single crystals, the temperature dependences of the dielectric constants and electrical conductivities were measured at frequencies of 0.3, 1, 3, and 5 MHz in the temperature range from 20° to 640 °C. Within this range, the dielectric constant does not reach a maximum, but near the phase-transition temperature at 587° C, the dielectric constant along the c axis shows a larger discontinuity than those along the a and b axes. The temperature dependence of the dielectric constant is consistent with the disordered structure of the high temperature form. Based on the parabolic increase of the dielectric constant in the temperature range from 582° to 587° C, it is likely that the phase transition propagates through an intermediate state. The electrical conductivity coefficients of K2SO4 increase with increasing temperature, exhibiting semiconducting character above the phase-transition temperature. In the high-temperature form, the electrical conductivity along the a axis exceeds that along the c axis. Since the electrical conductivity of K2SO4 is mainly ionic in character, the migration of K+ ions makes a major contribution to the conduction process.  相似文献   

4.
Microsommite, ideal formula [Na4K2(SO4)] [Ca2Cl2][Si6Al6O24], is a rare feldspathoid that occurs in volcanic products of Vesuvius. It belongs to the cancrinite–davyne group of minerals, presenting an ABAB… stacking sequence of layers that contain six-membered rings of tetrahedra, with Si and Al cations regularly alternating in the tetrahedral sites. The structure was refined in space group P63 to R=0.053 by means of single-crystal X-ray diffraction data. The cell parameters are a=22.161?Å=√3a dav, c=5.358?Å=c dav; Z=3. The superstructure arises due to the long-range ordering of extra-framework ions within the channels of the structure. This ordering progressively decreases with rising temperature until it is completely lost and microsommite transforms into davyne. The order–disorder transformation has been monitored in several crystals by means of X-ray superstructure reflections and the critical parameters T c?≈?750?°C and β?≈?0.12 were obtained. The kinetics of the ordering process were followed at different temperatures and the activation energy was determined to be about 125?kJ?mol?1. The continuous order–disorder phase transition in microsommite has been discussed on the basis of a two-dimensional Ising model in a triangular lattice with nn (nearest neighbours) and nnn (next-nearest neighbours) interactions. Such a model was simulated using a Monte Carlo technique. The theoretical model well matches the experimental data; two phase transitions were indicated by the simulated runs: at low temperature only one of the three sublattices begins to disorder, whereas the second transition involves all three sublattices.  相似文献   

5.
A modulation function representing the position and density of (Na, Ca) atoms in the superstructure of the e-plagioclase has been derived from the average structures of different plagioclase and a general modulation theory. Based on this function the superstructure of bytownite (An73) has been studied with the single crystal X-ray method. The cell dimensions by Megaw's axes are a=7.946(3)A, b=67.09(2)A, c=12.236(4)A, α=39.03(1)°, β=45.63(1)° and γ=59.63(1)°. Z=18(Na, Ca) Al(Al, Si)Si2O8. The initial phase factor of the modulation function for bytownite has been obtained from the intensity data of the satellite reflections. This modulation function indicates a coherent small-scale alternation of the Na-rich and Ca-rich bands in the superstructure. This superstructure has been refined by applying the albite and anorthite structures to the Na-rich and Ca-rich bands, respectively. The change of the superstructure of the e-plagioclase due to the compositional change has been described based on the movements of the satellites in reciprocal space. The direction of the coherent small-scale intergrowth of the anorthite-like and albite-like bands is perpendicular to the t vector. The thickness of the intergrowth is 1/|t|. Both direction and thickness change regularly from An75 to An25.  相似文献   

6.
MX-1 tridymite is one of the room-temperature polymorphs of SiO2 tridymite and has an underlying monoclinic structure (Cc) with incommensurate modulations along a * and c * (Hoffmann et al. 1983; Löns and Hoffmann 1987). With increasing temperature up to 500° C, MX-1 is reported to experience at least five structural phase transitions. However, its structures and the relationships to other tridymite polymorphs are unclear. We present here a 29Si MAS NMR study of the room-temperature incommensurate structure of MX-1 and its structural phase transitions up to 540° C. Our results suggest that at room temperature, all the Si sites in MX-1 tridymite are in positions with similiar ∠Si-O-Si of ～150° and are consistent with the presence of two incommensurate modulations proposed by Hoffmann et al. (1983). Simulations of the spectra yield modulation amplitudes of 1.33 and 0.87 ppm, corresponding to 0.009 and 0.006 Å for Si-Si. The maximum atomic displacements along a and b due to the modulations appear to be ～0.01–0.02 Å. The structural phase transitions of MX-1 are significantly different from those of MC tridymite below 220° C. Our high temperature results confirm that MX-1 tridymite transforms to the H5 phase at about 65° C. The most important transition occurs near 110° C, where the H5 phase transforms to a phase yielding a single, narrow NMR peak, indicating the disappearance of the superstructure and possibly the onset of the dynamic averaging. The NMR lineshapes of H5 are consistent with the metrically orthorhombic unit cell and commensurate superstructure of 2a, 2b and 10c proposed by Graetsch and Flörke (1991). The phase present above 110° C is probably similar to the OC phase, but has a mean ∠Si-O-Si of ～152.0° at 113° C, 152.9° at 185° C and 154.1° at 500° C. The transitions at ～160 and 220° C for MX-1 are subtle and probably due to impurity MC. Analysis of the modulations in the OS phase of MC tridymite indicates that their amplitudes are of the order of 0.02 Å, significantly less than the value 0.3 Å proposed by Nukui et al. (1979).  相似文献   

7.
X-ray diffraction and microprobe analyses of pseudomonocrystalline fragments of pyrrhotite from Bodenmais, Bavaria, revealed continuous gradients in composition and phase distribution. The gradients extend from the well-developed (0001) cleavage surfaces 15–30 μm into the bulk of the crystals. The phase gradient is made up two low-temperature pyrrhotites with monoclinic (4C) and hexagonal (5C) symmetry. The fraction of monoclinic pyrrhotite, expressed on the basis of recorded X-ray intensities, I, decreases exponentially according to I (mon)/[I (hex)+I (mon)] = EXP (aX+b) where a is a constant ranging from ?0.04 to ?0.25, X is the depth from the (0001) cleavage surface in μm, and b is a constant determined by the intensity ratios obtained from the untreated cleavage surfaces. The phase gradient developed during retrograde reactions from a continuous composition gradient. This primary gradient was caused by the extraction of iron from a disordered, high-temperature hexagonal pyrrhotite during oxidation of the cleavage surfaces at temperatures above 254° C (upper stability limit of 4C pyrrhotite), probably above 308° C. The length of the c axis of the monoclinic superstructure slightly increases with the increase in iron and decrease in vacancy content of the bulk. This expansion is probably due to a minor compositional variation of the monoclinic phase controlled by the availability of vacancies during the transition to low-temperature phases.  相似文献   

8.
《Geochimica et cosmochimica acta》1999,63(13-14):1969-1980
The solubility of ettringite (Ca6[Al(OH)6]2(SO4)3 · 26H2O) was measured in a series of dissolution and precipitation experiments at 5–75°C and at pH between 10.5 and 13.0 using synthesized material. Equilibrium was established within 4 to 6 days, with samples collected between 10 and 36 days. The log KSP for the reaction Ca6[Al(OH)6]2(SO4)3 · 26H2O ⇌ 6Ca2+ + 2Al(OH)4− + 3SO42− + 4OH− + 26H2O at 25°C calculated for dissolution experiments (−45.0 ± 0.2) is not significantly different from the log KSP calculated for precipitation experiments (−44.8 ± 0.4) at the 95% confidence level. There is no apparent trend in log KSP with pH and the mean log KSP,298 is −44.9 ± 0.3. The solubility product decreased linearly with the inverse of temperature indicating a constant enthalpy of reaction from 5 to 75°C. The enthalpy and entropy of reaction ΔH°r and ΔS°r, were determined from the linear regression to be 204.6 ± 0.6 kJ mol−1 and 170 ± 38 J mol−1 K−1. Using our values for log KSP, ΔH°r, and ΔS°r and published partial molal quantities for the constituent ions, we calculated the free energy of formation ΔG°f,298, the enthalpy of formation ΔH°f,298, and the entropy of formation ΔS°f,298 to be −15211 ± 20, −17550 ± 16 kJ mol−1, and 1867 ± 59 J mol−1 K−1. Assuming ΔCP,r is zero, the heat capacity of ettringite is 590 ± 140 J mol−1 K−1.  相似文献   

9.
A synthetic clinopyroxene with composition LiFe3+Ge2O6, monoclinic s.g. P21/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) Å3, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P21/c to C2/c at a transition temperature T tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe3+Ge2O6, monoclinic s.g. P21/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?3, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P21/c to C2/c at a transition temperature T tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P21/c expands more than the C2/c phase. The evolution of Q 2 (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q 02 = 0.538(2) at T tr, with T c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe3+Si2O6) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P21/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T tr [206.8(5)° at 703 K] and extends by 12° at the transition.  相似文献   

10.
In situ high-temperature synchrotron radiation powder diffraction patterns were taken from room temperature to T = 740°C from synthetic feldspars along the join CaAl2Si2O8–SrAl2Si2O8 (An–SrF). Three samples of composition An95SrF5, An90SrF10 and An85SrF15 were investigated, and the evolution of cell parameters with T was determined by Rietveld analysis of powder X-ray diffraction patterns. The high-temperature $P\bar 1{\text{-}}I\bar 1$ phase transition, previously observed with T c = 241°C in anorthite, was found in An95SrF5, An90SrF10 and An85SrF15 feldspars at T c = 233(5)°, 195(2)° and 174(2)°C respectively. The transition was revealed by the disappearance of critical reflections and variations in the rate of change of cell parameters with temperature. A significant, although small (between 0.0025 and 0.0012 at room temperature), spontaneous strain could be measured, allowing the thermodynamic behaviour of the transition to be modelled. A second-order trend for An90SrF10 and An85SrF15 [β = 0.504(7) and 0.505(7) respectively] or nearly second-order for An95SrF5[β = 0.458(4)] was observed in contrast with tricritical behaviour of end member anorthite. An extrapolation of the T c versus composition to room temperature indicates that the critical composition for the $P\bar 1$ phase is An60SrF40.  相似文献   

11.
The temperature dependences of the crystal structure and superstructure intensities in sodium nitrate, mineral name nitratine, NaNO3, were studied using Rietveld structure refinements based on synchrotron powder X-ray diffraction. Nitratine transforms from $R{\overline{3}} c\;\hbox{to}\;R{\overline{3}} m$ at T c = 552(1) K. A NO3 group occupies, statistically, two positions with equal frequency in the disordered $R{\overline{3}} m$ phase, but with unequal frequency in the partially ordered $R{\overline{3}} c$ phase. One position for the NO3 group is rotated by 60° or 180° with respect to the other. The occupancy of the two orientations in the $R{\overline{3}} c$ phase is obtained from the occupancy factor, x, for the O1 site and gives rise to the order parameter, S = 2x ? 1, where S is 0 at T c and 1 at 0 K. The NO3 groups rotate in a rapid process from about 541 to T c, where the a axis contracts. Using a modified Bragg–Williams model, a good fit was obtained for the normalized intensities (that is, normalized, NI1/2) for the (113) and (211) reflections in $R{\overline{3}} c\hbox {\,NaNO}_{3},$ and indicates a second-order transition. Using the same model, a reasonable fit was obtained for the order parameter, S, and also supports a second-order transition.  相似文献   

12.
The P21/c clinopyroxene kanoite (ideally MnMgSi2O6) was studied as a function of pressure and temperature using powder X-ray diffraction, differential scanning calorimetry (DSC) and optical methods. The temperature of the P21/c to high-temperature (HT) C2/c transition ranges from 425?°C in endmember MnMgSi2O6 to 125?°C in natural samples with an aegirine component. Compiling pigeonite and clinoenstatite–clinoferrosilite literature data, the temperature of the transformation was found to decrease linearly with M2 cation size. A synchrotron powder diffraction study in a heated diamond-anvil cell (DAC) yielded compression and thermal expansion data for low kanoite of composition Mn1.2Mg0.4Fe0.4Si2O6. The high-pressure (HP) phase transition from P21/c to HPC2/c was reversed at 5.8 GPa at 417?°C. The high-temperature phase transition from P21/c to HTC2/c was rather indistinct and occurred at approximately 530?°C and 0.76 GPa. In a separate experiment, the HT transition was observed optically in a hydrothermal DAC between 0.0 and 0.4 GPa. The in-situP-T data of both experiments yielded an increase in transition temperature with increasing pressure (approx. 149?°C/GPa) and suggest a change in character of the transition from first order to continuous with increasing pressure. The data indicate that the HTC2/c and HPC2/c polymorphs are distinct phases with different stability fields. Since the high-temperature and the high-pressure polymorphs of kanoite were shown to be isotypic with other low-Ca clinopyroxenes such as the (Mg,Fe)SiO3 series, the conclusions we draw from this study are valid for all clinopyroxenes with small (<0.88 Å) M1 and M2 cation sizes. The petrologic implications of these conclusions for the occurrence of “clinoenstatite” in the Alpe Arami peridotite are discussed.  相似文献   

13.
Using a DIA-type, cubic-anvil, high-pressure apparatus (SAM-85) in conjunction with in situ X-ray diffraction, we have investigated phase relations between coesite and stishovite up to 12 GPa and 1530 °C using synthetic powders of the two phases as the starting materials. The phase transition between coesite and stishovite was identified by observing the first appearance of a phase that did not already exist or by a change in the relative intensity of the two patterns. In most experiments, the diffraction patterns on samples were collected within 10 minutes after reaching a pressure and temperature condition. On this time scale, two phase boundaries associated with the coesite-stishovite transition have been determined: (1) for the stishovite-to-coesite transition, observations were made in the temperature range of 950–1530 °C, and (2) for the coesite-to-stishovite transition from 500 to 1300 °C. These observations reveal that there exists a critical temperature of about 1000 °C to constrain the coesite-stishovite equilibrium phase boundary. Above this temperature, both boundaries are linear, have positive dP/dT slopes, and lie within a pressure interval of 0.4 GPa. Below this temperature, the dP/dT slope for the stishovite-to-coesite phase boundary becomes significantly larger and that for the coesite-tostishovite phase boundary changes from positive to negative. As a result, an equilibrium phase boundary can only be determined from the results above 1000 °C and is described by a linear equation P (GPa)=6.1 (4)+ 0.0026 (2) T (°C). This dP/dT slope is in good agreement with that of Zhang et al. (1993) but more than twice that of Yagi and Akimoto (1976). For the kinetics of the phase transition, preliminary rate data were obtained for the stishovite-to-coesite transition at 1160 and 1430 °C and are in agreement with the simple geometric transformation model of Avrami and Cahn.  相似文献   

14.
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   

15.
In situ high-pressure investigations on norsethite, BaMg(CO3)2, have been performed in sequence of diamond-anvil cell experiments by means of single-crystal X-ray and synchrotron diffraction and Raman spectroscopy. Isothermal hydrostatic compression at room temperature yields a high-pressure phase transition at P c ≈ 2.32 ± 0.04 GPa, which is weakly first order in character and reveals significant elastic softening of the high-pressure form of norsethite. X-ray structure determination reveals C2/c symmetry (Z = 4; a = 8.6522(14) Å, b = 4.9774(13) Å, c = 11.1542(9) Å, β = 104.928(8)°, V = 464.20(12) Å3 at 3.00 GPa), and the structure refinement (R 1 = 0.0763) confirms a distorted, but topologically similar crystal structure of the so-called γ-norsethite, with Ba in 12-fold and Mg in octahedral coordination. The CO3 groups were found to get tilted off the ab-plane direction by ~16.5°. Positional shifts, in particular of the Ba atoms and the three crystallographically independent oxygen sites, give a higher flexibility for atomic displacements, from which both the relatively higher compressibility and the remarkable softening originate. The corresponding bulk moduli are K 0 = 66.2 ± 2.3 GPa and dK/dP = 2.0 ± 1.8 for α-norsethite and K 0 = 41.9 ± 0.4 GPa and dK/dP = 6.1 ± 0.3 for γ-norsethite, displaying a pronounced directional anisotropy (α: β a ?1  = 444(53) GPa, β c ?1  = 76(2) GPa; γ: β a ?1  = 5.1(1.3) × 103 GPa, β b ?1  = 193(6) GPa β c ?1  = 53.4(0.4) GPa). High-pressure Raman spectra show a significant splitting of several modes, which were used to identify the transformation in high-pressure high-temperature experiments in the range up to 4 GPa and 542 K. Based on the experimental series of data points determined by XRD and Raman measurements, the phase boundary of the α-to-γ-transition was determined with a Clausius–Clapeyron slope of 9.8(7) × 10?3 GPa K?1. An in situ measurement of the X-ray intensities was taken at 1.5 GPa and 411 K in order to identify the nature of the structural variation on increased temperatures corresponding to the previously reported transformation from α- to β-norsethite at 343 K and 1 bar. The investigations revealed, in contrast to all X-ray diffraction data recorded at 298 K, the disappearance of the superstructure reflections and the observed reflection conditions confirm the anticipated \(R\bar{3}m\) space-group symmetry. The same superstructure reflections, which disappear as temperature increases, were found to gain in intensity due to the positional shift of the Ba atoms in the γ-phase.  相似文献   

16.
The phase transition of Mg2GeO4 from the olivine structure (α-phase) to the spinel structure (γ-phase) was determined by complex electrical resistivity measurements in the frequency range 10 Hz up to 100 kHz. The stability fields of the α- and the γ-phase were confirmed up to 2.05 GPa in the temperature range 845° C–1400° C. Based on volume resistivity data, a decrease of about a factor of 5 was found at the α-γ phase transition. Activation energies of electrical conduction E a at 1.05 GPa and 2.05 GPa were calculated using the volume resistivities (?) and the relaxation times (τ). The values range from 1.98 eV up to 2.78 eV. The relative dielectric permeability increases with increasing temperature. This is is due to crystal defects and charge transport mechanisms.  相似文献   

17.
Methods have been developed for solution calorimetry of hydrous phases in molten lead borate near 700°C. These involve thermochemical cycles using dissolution and decomposition reactions of hydrous silicates and hydroxides. Preliminary results suggest that H2O derived from the decomposition of hydroxides dissolves in molten 2PbO-B2O3 with an exothermic enthalpy of solution of −5.7 ±0.7 kcal mol−1. Hydroxyphologopite persists metastably at 714°C and its heat of solution in 2PbO·B2O3 has been measured. From these new data, the standard enthalpy of formation of phlogopite from the elements at 25°C is −1485.5 ±1.5 kcal mol−1. The standard free energy of formation is -1394.6 ±1.5 kcal mol−1, assuming complete tetrahedral Al-Si disorder.Two structural features complicate the thermodynamics of synthetic and natural micas. The first is a varying degree of tetrahedral Al-Si disorder. Raman spectroscopic study of phlogopite synthesized above 600°C suggests a disordered Al-Si distribution. Calculations of the P-T locus of the geologically important equilibrium: Phl + 3Qtz = 3En + Sa + H2O, using our thermochemical data, agree within experimental error with the results of calculations based on the best available phase equilibrium data only if a tetrahedrally disordered phlogopite is assumed. Such calculations are very sensitive to uncertainties in ΔH° and ΔG°, and reversed phase equilibrium experiments remain essential to obtaining reliable estimates of thermodynamic properties. In contrast to these Al-Si disordered phlogopites, some biotites of low temperature parageneses (<600°C) may have substantial Al-Si order. A variable Al-Si distribution has a substantial effect on the configurational entropy and therefore on the free energy of the mica in question. Because of these and other questions, applications of biotite equilibria to determining volatile fugacities in igneous and metamorphic petrogenesis are subject to large uncertainties.The second structural complication is stacking disorder, which is present in phlogopite synthesized at 650°C but not in the 850°C sample. The enthalpy difference between these two samples, determined by solution calorimetry, is smaller than the experimental uncertainty of ±1.0 kcal mol−1. Thus there appears to be little driving force for ordering, and micas with disordered stacking sequences may persist in many geologic environments. The effect of stacking disorder on thermodynamic properties is probably very small.  相似文献   

18.
On heating the paramagnetic clay mineral nontronite for ≈ 30 h at 970 °C in air, a new ferrimagnetic phase forms which was studied by magnetic techniques, microprobe analysis, x-ray diffraction and Mössbauer spectroscopy. The new phase has a Curie temperature T c ≈ 240°C and high magnetic anisotropy at room temperature with a spontaneous magnetization >12 Am2/kg. Semiquantitative microprobe analyses show Fe to be the dominating consistuent. X-ray analysis points to a lattice which may be similar to that of ?-Fe2O3 but differs from it in detail. 57Fe Mössbauer spectra, taken between 78 K and 295 °C, can be deconvoluted into three sextet subpatterns in the ferrimagnetic region which are well resolved at room temperature and exhibit a rather small line width. Above T c, a doublet is visible which is typical for Fe3+ ions.  相似文献   

19.
Single crystals of Li-aegirine LiFe3+Si2O6 were synthesized at 1573?K and 3?GPa, and a polycrystalline sample suitable for neutron diffraction was produced by ceramic sintering at 1223?K. LiFe3+Si2O6 is monoclinic, space group C2/c, a=9.6641(2)?Å, b= 8.6612(3)?Å, c=5.2924(2)?Å, β=110.12(1)° at 300?K as refined from powder neutron data. At 229?K Li-aegirine undergoes a phase transition from C2/c to P21 /c. This is indicated by strong discontinuities in the temperature variation of the lattice parameters, especially for the monoclinic angle β and by the appearance of Bragg reflections (hkl) with h+k≠2n. In the low-temperature form two non-equivalent Si-sites with 〈SiA–O〉=1.622?Å and 〈SiB–O〉=1.624?Å at 100?K are present. The bridging angles of the SiO4 tetrahedra O3–O3–O3 are 192.55(8)° and 160.02(9)° at 100?K in the two independent tetrahedral chains in space group P21 /c, whereas it is 180.83(9)° at 300?K in the high-temperature C2/c phase, i.e. the chains are nearly fully expanded. Upon the phase transition the Li-coordination changes from six to five. At 100?K four Li–O bond lengths lie within 2.072(4)–2.172(3)?Å, the fifth Li–O bond length is 2.356(4)?Å, whereas the Li–O3?A bond lengths amount to 2.796(4)?Å. From 57Fe Mössbauer spectroscopic measurements between 80 and 500?K the structural phase transition is characterized by a small discontinuity of the quadrupole splitting. Temperature-dependent neutron powder diffraction experiments show first occurrence of magnetic reflections at 16.5?K in good agreement with the point of inflection in the temperature-dependent magnetization of LiFe3+Si2O6. Distinct preordering phenomena can be observed up to 35?K. At the magnetic phase transition the unit cell parameters exhibit a pronounced magneto-striction of the lattice. Below T N Li-aegirine shows a collinear antiferromagnetic structure. From our neutron powder diffraction experiments we extract a collinear antiferromagnetic spin arrangement within the a–c plane.  相似文献   

20.
The ordering of Al and Si in Mg cordierite Mg2Al4Si5O18 is considered using computer simulation. First the enthalpy of interaction J ij between sites is derived by computer modelling 101 different Al/Si configurations and analysing their energies. They are compared with similar results for three other minerals and with ab initio calculations to assess the whole approach. Secondly the ordering process is studied using Monte Carlo simulation applied to the J ij . The ordering phase transition temperature T c is found as 1800°C in reasonable agreement with the experimental estimate of 1450° C. These are much lower than the estimate T c(ABW)≈7600°C obtained from Bragg-Williams theory. Strong short-range order sets in below T c(ABW), and the reasons for much lower temperature T c of long-range ordering are discussed. Strong short-range also sets in very rapidly in a simulated anneal, in agreement with experiment. Thirdly an attempt is made to compare our calculated enthalpies directly with the results of NMR and calorimetry experiments, not completely successfully. A free energy ΔG≈4.6 eV for the activation barrier for ordering is suggested.  相似文献   

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