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1.
The electrical conductivities of alkali feldspar solid solutions ranging in chemical composition from albite (NaAlSi3O8) to K-feldspar (KAlSi3O8) were measured at 1.0 GPa and temperatures of 873–1,173 K in a multi-anvil apparatus. The complex impedance was determined by the AC impedance spectroscopy technique in the frequency range of 0.1–106 Hz. Our experimental results revealed that the electrical conductivities of alkali feldspar solid solutions increase with increasing temperature, and the linear relationship between electrical conductivity and temperature fits the Arrhenius formula. The electrical conductivities of solid solutions increase with the increasing Na content at constant temperature. At 1.0 GPa, the activation enthalpy of solid solution series shows strong dependency on the composition, and there is an abrupt increase from the composition of Or40Ab60 to Or60Ab40, where it reaches a value of 0.96 eV. According to these results in this study, it is proposed that the dominant conduction mechanism in alkali feldspar solid solutions under high temperature and high pressure is ionic conduction. Furthermore, since the activation enthalpy is less than 1.0 eV for the alkali feldspar solid solutions, it is suggested to be a model where Na+ and K+ transport involves an interstitial mechanism for electrical conduction. The change of main charge carriers can be responsible for the abrupt increase in the activation energy for Or60Ab40. All electrical conductivity data were fitted by a general formula in order to show the dependence of activation enthalpy and pre-exponential factor on chemical composition. Combining our experimental results with the effective medium theory, we theoretically calculated the electrical conductivity of alkali feldspar granite, alkali feldspar quartz syenite, and alkali feldspar syenite with different mineral content and variable chemical composition of alkali feldspar at high temperatures at 1.0 GPa, and the calculated results are almost in agreement with previous experimental studies on silicate rocks.  相似文献   

2.
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3.
Mineralogical analysis, electrical conductivity and thermopower are reported for monocrystalline heterosite (Fe3+, Mn3+)PO4 with the orthorhombic olivine-type structure. The 57Fe Mössbauer spectrum could be adequately described using two Fe3+ doublets. By impedance spectroscopy (20 Hz–1 MHz) the electrical DC conductivity σDC and AC conductivity σAC were determined parallel (∥) and perpendicular to the [001] direction (space group Pnma) in the range ～160–440 K. The graph log σDC?1/T shows a slightly bent curve in both directions with activation energies of E A ～0.30 and ～0.15 eV in the high and low temperature ranges, respectively. The reduced E A is associated with electronic conduction; σDC ∥ [001] follows Mott’s T 1/4 variable range hopping law at lower temperatures with hopping between localized levels. The values of σAC are increased relative to σDC at high frequencies and low temperatures, obeying Jonscher’s universal dynamic response law; for σAC ∥ [001], the variation with temperature of the frequency exponent is in fair agreement with the model of small polaron hopping. The absolute thermopower Θ is negative and low between ～295 and ～440 K, Θ does hardly vary with temperatures in both directions; the temperature independency of Θ ∥ [001] is consistent with the small polaron hopping model.  相似文献   

4.
The electrical conductivity of monocrystalline triphylite, Li(Fe2+,Mn2+)PO4, with the orthorhombic olivine-type structure was measured parallel (∥) to the [010] direction and ∥ [001] (space group Pnma), between ～400 and ～700 K. Electrical measurements on triphylite are of technological interest because LiFePO4 is a promising electrode material for rechargeable Li batteries. Triphylite was examined by electron microprobe, ICP atomic emission spectroscopy, X-ray diffraction, Mössbauer spectroscopy and microscopic analysis. The DC conductivity σDC was determined from AC impedance data (20 Hz–1 MHz) extrapolating to zero frequency. Triphylite shows σDC with activated behavior measured ∥ [010] between ～500 and ～700 K during the first heating up, with activation energy of E A = 1.52 eV; on cooling E A = 0.61 eV was found down to ～400 K and extrapolated σDC (295 K) ～10?9 Ω?1cm?1; ∥ [001] E A = 0.65 eV and extrapolated σDC(295 K) ～10?9 to 10?10 Ω?1cm?1, measured during the second heating cycle. The enhanced AC conductivity relative to σDC at lower temperatures indicates a hopping-type charge transport between localized levels. Conduction during the first heating up is ascribed to ionic Li+ hopping. DC polarization experiments showed conduction after the first heating up to be electronic related to lowered activation energy. Electronic conduction appears to be coupled with the presence of Li+ vacancies and Fe3+, formed by triphylite alteration. For comparison, σDC was measured on the synthetic compound LiMgPO4 with olivine-type structure, where also an activated behavior of σDC with E A ～1.45 eV was observed during heating and cooling due to ionic Li+ conduction; here no oxidation can occur associated with formation of trivalent cations.  相似文献   

5.
1 Introduction recognized and accepted by more and more experts engaged in experimental research at high temperature and In-situ laboratory measurement of the electricity of high pressure. This method has been regardedgeological materials at high temperature and high pressure internationally as the most advanced one for the in-situis an important approach to revealing the composition, laboratory measurement of the electric properties ofstructure and properties of materials in the deep interior…  相似文献   

6.
Deformation experiments on olivine aggregates were performed under hydrous conditions using a deformation-DIA apparatus combined with synchrotron in situ X-ray observations at pressures of 1.5–9.8 GPa, temperatures of 1223–1800 K, and strain rates ranging from 0.8 × 10?5 to 7.5 × 10?5 s?1. The pressure and strain rate dependencies of the plasticity of hydrous olivine may be described by an activation volume of 17 ± 6 cm3 mol?1 and a stress exponent of 3.2 ± 0.6 at temperatures of 1323–1423 K. A comparison between previous data sets and our results at a normalized temperature and a strain rate showed that the creep strength of hydrous olivine deformed at 1323–1423 K is much weaker than that for the dislocation creep of water-saturated olivine and is similar to that for diffusional creep and dislocation-accommodated grain boundary sliding, while dislocation microstructures showing the [001] slip or the [001](100) slip system were developed. At temperatures of 1633–1800 K, a much stronger pressure effect on creep strength was observed for olivine with an activation volume of 27 ± 7 cm3 mol?1 assuming a stress exponent of 3.5, water fugacity exponent of 1.2, and activation energy of 520 kJ mol?1 (i.e., power-law dislocation creep of hydrous olivine). Because of the weak pressure dependence of the rheology of hydrous olivine at lower temperatures, water weakening of olivine could be effective in the deeper and colder part of Earth’s upper mantle.  相似文献   

7.
Electrical conductivity of talc was measured at 0.5 GPa and ~473 to ~1,300 K by using impedance spectroscopy both before and after dehydration. Before dehydration, the electrical conductivity of talc increased with temperature and is ~10?4 S/m at 1,078 K. After dehydration, most of the talc changed to a mixture of enstatite and quartz and the total water content is reduced by a factor 6 or more. Despite this large reduction in the total water content, the electrical conductivity increased. The activation enthalpy of electrical conductivity (~125 kJ/mol) is too large for the conduction by free water but is consistent with conduction by small polaron. Our results show that a majority of hydrogen atoms in talc do not enhance electrical conductivity, implying the low mobility of the hydrogen atoms in talc. The observed small increase in conductivity after dehydration may be attributed to the increase in oxygen fugacity that enhances conductivity due to small polaron.  相似文献   

8.
As part of a study of ion migration mechanisms in feldspars, the dynamical behaviour of the alkali metal cations ions in albite and K-feldspar has been investigated using a combination of dielectric spectroscopy and atomistic computer simulation techniques. The low-frequency dielectric properties of these minerals have been studied from room temperature to 1100 K. At each temperature, the dielectric constant, conductivity and dielectric loss were determined over a range of frequencies from 100 Hz to 10 MHz. At high temperatures a distinct Debye-type relaxation in the dielectric loss spectra was observed for both albite and K-feldspar; the activation energy for these processes was determined to be 1.33 eV in both albite and K–feldspar. Atomistic simulation techniques were used to elucidate the mechanism and energetics of the cation migration processes. Mechanisms involving the conventional hopping of Na+ and K+ ions between cation sites in the (010) plane were found to give calculated energy barriers in good agreement with the experimentally determined activation energies. These results assist in understanding the nature of the processes responsible for the observed dielectric behaviour.  相似文献   

9.
We performed in situ infrared spectroscopic measurements of OH bands in a forsterite single crystal between ?194 and 200 °C. The crystal was synthesized at 2 GPa from a cooling experiment performed between 1,400 and 1,275 °C at a rate of 1 °C per hour under high silica-activity conditions. Twenty-four individual bands were identified at low temperature. Three different groups can be distinguished: (1) Most of the OH bands between 3,300 and 3,650 cm?1 display a small frequency lowering (<4 cm?1) and a moderate broadening (<10 cm?1) as temperature is increased from ?194 to 200 °C. The behaviour of these bands is compatible with weakly H-bonded OH groups associated with hydrogen substitution into silicon tetrahedra; (2) In the same frequency range, two bands at 3,617 and 3,566 cm?1 display a significantly anharmonic behaviour with stronger frequency lowering (42 and 27 cm?1 respectively) and broadening (~30 cm?1) with increasing temperature. It is tentatively proposed that the defects responsible for these OH bands correspond to H atoms in interstitial position; (3) In the frequency region between 3,300 and 3,000 cm?1, three broad bands are identified at 3,151, 3,178 and 3,217 cm?1, at ?194 °C. They exhibit significant frequency increase (~20 cm?1) and broadening (~70 cm?1) with increasing temperature, indicating moderate H bonding. These bands are compatible with (2H)Mg defects. A survey of published spectra of forsterite samples synthesized above 5 GPa shows that about 75 % of the incorporated hydrogen belongs to type (1) OH bands associated with Si substitution and 25 % to the broad band at 3,566 cm?1 (type (2); 3,550 cm?1 at room temperature). The contribution of OH bands of type (3), associated to (2H)Mg defects, is negligible. Therefore, solubility of hydrogen in forsterite (and natural olivine compositions) cannot be described by a single solubility law, but by the combination of at least two laws, with different activation volumes and water fugacity exponents.  相似文献   

10.
In order to investigate the origin of the high conductivity anomalies geophysically observed in the mid-lower crust of Tibet Plateau, the electrical conductivity of plagioclase–NaCl–water system was measured at 1.2 GPa and 400–900 K. The relationship between electrical conductivity and temperature follows the Arrhenius law. The bulk conductivity increases with the fluid fraction and salinity, but is almost independent of temperature (activation enthalpy less than 0.1 eV). The conductivity of plagioclase–NaCl–water system is much lower than that of albite–NaCl–water system with similar fluid fraction and salinity, indicating a strong effect of the major mineral phase on the bulk conductivity of the brine-bearing system. The high conductivity anomalies of 10?1 and 100 S/m observed in the mid-lower crust of Tibet Plateau can be explained by the aqueous fluid with a volume fraction of 1 and 9%, respectively, if the fluid salinity is 25%. The anomaly value of 10?1 S/m can be explained by the aqueous fluid with a volume fraction of 6% if the salinity is 10%. In case of Southern Tibet where the heat flow is high, the model of a thin layer of brine-bearing aqueous fluid with a high salinity overlying a thick layer of partial melt is most likely to prevail.  相似文献   

11.
Three different types of permeability tests were conducted on 23 intact and singly jointed rock specimens, which were cored from rock blocks collected from a rock cavern under construction in Singapore. The studied rock types belong to inter-bedded meta-sandstone and meta-siltstone with very low porosity and high uniaxial compressive strength. The transient pulse water flow method was employed to measure the permeability of intact meta-sandstone under a confining pressure up to 30 MPa. It showed that the magnitude order of meta-sandstone’s intrinsic permeability is about 10?18 m2. The steady-state gas flow method was used to measure the permeability of both intact meta-siltstone and meta-sandstone in a triaxial cell under different confining pressures spanning from 2.5 to 10 MPa. The measured permeability of both rock types ranged from 10?21 to 10?20 m2. The influence of a single natural joint on the permeability of both rock types was studied by using the steady-state water flow method under different confining pressures spanning from 1.25 to 5.0 MPa, including loading and unloading phases. The measured permeability of both jointed rocks ranged from 10?13 to 10?11 m2, where the permeability of jointed meta-siltstone was usually slightly lower than that of jointed meta-sandstone. The permeability of jointed rocks decreases with increasing confining pressure, which can be well fitted by an empirical power law relationship between the permeability and confining pressure or effective pressure. The permeability of partly open cracked specimens is lower than that of open cracked specimens, but it is higher than that of the specimen with a dominant vein for the meta-sandstone under the same confining pressure. The permeability of open cracked rock specimens will partially recover during the unloading confining pressure process. The equivalent crack (joint) aperture is as narrow as a magnitude order of 10?6 m (1 μm) in the rock specimens under confining pressures spanning from 1.25 to 5.0 MPa, which represent the typical ground stress conditions in the cavern. The in situ hydraulic conductivity measurements conducted in six boreholes by the injection test showed that the in situ permeability of rock mass varies between 10?18 and 10?11 m2. The lower bound of the in situ permeability is larger than that of the present laboratory-tested intact rock specimens, while the upper bound of the in situ permeability is less than that of the present laboratory-tested jointed rock specimens. The in situ permeability test results were thus compatible with our present laboratory permeability results of both intact and jointed rock specimens.  相似文献   

12.
Recently, the thermal fluid loop has been established and continuosly operated for 7 days at the geothermal in situ laboratory in Groß Schönebeck (North German Basin). During this initial phase of fluid production, the fluid temperature, measured at the surface, continuously increased until a stable value of about 98 °C was established. Fluid physicochemical properties (pH, redox, density, temperature, and pressure) were measured online and in situ with a newly developed fluid monitoring system (FluMo). Additionally, fluid samples have been collected at various temperatures (in 5–10 °C steps) directly at the production well at about 10 bar pressure. From the pressurized sampling tool, the fluid was directly transferred into a heated autoclave, which allowed filtration (0.2 μm) in the absence of oxygen. Physicochemical parameters [pH, redox, electric conductivity, total dissolved solids (TDS)] as well as acid capacity (K S 4.3) of these samples have been measured onsite at atmospheric conditions. Concentrations of anions, total organic carbon, and metals were analyzed later in the laboratory. Both, measurements in collected samples or in situ (FluMo) analysis of most the parameters density, electric conductivity, or TDS indicated relatively constant values over the whole production time (1.17–1.18 g · cm?3, 215–221 mS · cm?1, 241–260 g · L?1, respectively). Good correlation was also found for pH values (pH = 6.6–6.9), whereas the redox values varied between ?1 and 46 mV when determined at 25 °C and decreased strongly when measured in situ with increasing temperature (?110 mV at 90 °C). The elemental composition of collected samples remained also relatively constant for most compounds and was clearly higher as compared with samples collected in 2011. Results of this study demonstrate that realistic, comprehensive, and time-resolved physicochemical data can be obtained by FluMo. These detailed data sets can be crucial to understand the complex geochemical processes in a thermal water loop and eventually to take required measures on time.  相似文献   

13.
The speciation of CO2 in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO2 into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO2 re-appeared. Infrared extinction coefficients of both carbonate and molecular CO2 decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/t = 0.98) and basaltic andesite (NBO/t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/t = 0.09) and phonolite melts (NBO/t = 0.14), the equilibrium CO2 + O2? = CO3 2? in the melt shifts toward CO2 with increasing temperature, with ln K = ?4.57 (±1.68) + 5.05 (±1.44) 103 T ?1 for dacite melt (ΔH = ?42 kJ mol?1) and ln K = ?6.13 (±2.41) + 7.82 (±2.41) 103 T ?1 for phonolite melt (ΔH = ?65 kJ mol?1), where K is the molar ratio of carbonate over molecular CO2 and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that ΔS and ΔH are linear functions of NBO/t. Based on this relationship, a general model for CO2 speciation in silicate melts is developed, with ln K = a + b/T, where T is temperature in Kelvin and a = ?2.69 ? 21.38 (NBO/t), b = 1,480 + 38,810 (NBO/t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO2, and therefore, the diffusion coefficient of CO2 is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO2 solubility and speciation on melt composition, in accordance with available solubility data.  相似文献   

14.
The in situ electrical conductivity of hydrous garnet samples (Py20Alm76Grs4–Py73Alm14Grs13) was determined at pressures of 1.0–4.0 GPa and temperatures of 873–1273 K in the YJ-3000t apparatus using a Solartron-1260 impedance/gain-phase analyzer for various chemical compositions and oxygen fugacities. The oxygen fugacity was controlled by five solid-state oxygen buffers (Fe2O3 + Fe3O4, Ni + NiO, Fe + Fe3O4, Fe + FeO, and Mo + MoO2). Experimental results indicate that within a frequency range from 10−2 to 106 Hz, electrical conductivity is strongly dependent on signal frequency. Electrical conductivity shows an Arrhenius increase with temperature. At 2.0 GPa, the electrical conductivity of anhydrous garnet single crystals with various chemical compositions (Py20Alm76Grs4, Py30Alm67Grs3, Py56Alm43Grs1, and Py73Alm14Grs13) decreases with increasing pyrope component (Py). With increasing oxygen fugacity, the electrical conductivity of dry Py73Alm14Grs13 garnet single crystal shows an increase, whereas that of a hydrous sample with 465 ppm water shows a decrease, both following a power law (exponents of 0.061 and −0.071, respectively). With increasing pressure, the electrical conductivity of this hydrous garnet increases, along with the pre-exponential factors, and the activation energy and activation volume of hydrous samples are 0.7731 ± 0.0041 eV and −1.4 ± 0.15 cm3/mol, respectively. The results show that small hopping polarons ( \textFe\textMg · ) \left( {{\text{Fe}}_{\text{Mg}}^{ \cdot } } \right) and protons ( \textH · {\text{H}}^{ \cdot } ) are the dominant conduction mechanisms for dry and wet garnet single crystals, respectively. Based on these results and the effective medium theory, we established the electrical conductivity of an eclogite model with different mineral contents at high temperatures and high pressures, thereby providing constraints on the inversion of field magnetotelluric sounding results in future studies.  相似文献   

15.
We have measured the isotropic chemical shifts (δiso) and the spin-lattice relaxation times (T1) for 17O and 25Mg in MgO from room temperature up to 1300° C. The 17O chemical shifts increase linearly from 47 ppm at room temperature to 57 ppm at 1300° C, and over the same temperature range the 25Mg chemical shift increases linearly from 25 to 27 ppm. These changes are not the result of changes in the bulk magnetic susceptibility of the samples, but may be due to increased orbital overlap which is the result of the increase in thermal vibration of the ions with temperature. In the case of 25Mg, the shift to lower shielding with increasing temperature is opposite to that expected from simple bond length versus chemical shift trends established for the oxides at room temperature. If this is a general phenomenon, high-temperature NMR data may be biased to lower shielding. Spin-lattice relaxation times (T1) were measured in order to study the energetics of defect motion. T1's for 17O and 25Mg exhibit similar behavior over the range of temperatures studied. Up to 800° C, T1's decrease gradually, but above 800° C, T1's drop rapidly, with slopes corresponding to apparent activation energies of 192±9 kJ/mol (2.0±0.1 eV) for 17O and 151±6 kJ/mol (1.56±0.06 eV) for 25Mg. While direct comparison of these activation energies to those derived from diffusion or conductivity measurements is complicated, the similar behavior for both nuclei suggests their relaxation phenomena are related.  相似文献   

16.
Ground-source geothermal systems are drawing increasing attention and popularity due to their efficiency, sustainability and being implementable worldwide. Consequently, design software and regulatory guidelines have been developed. Interaction with the subsurface significantly affects the thermal performance, sustainability, and impacts of such systems. Reviewing the related guidelines and the design software, room for improvement is evident, especially in regards to interaction with groundwater movement. In order to accurately evaluate the thermal effect of system and hydrogeological properties on a borehole heat exchanger, a fully discretized finite-element model is used. Sensitivity of the loop outlet temperatures and heat exchange rates to hydrogeological, system and meteorological factors (i.e. groundwater flux, thermal conductivity and volumetric heat capacity of solids, porosity, thermal dispersivity, grout thermal conductivity, background and inlet temperatures) are analyzed over 6-month and 25-year operation periods. Furthermore, thermal recovery during 25  years after system decommissioning has been modeled. The thermal plume development, transport and dissipation are also assessed. This study shows the importance of subsurface thermal conductivity, groundwater flow (flux > 10?7 m/s), and background and inlet temperature on system performance and impact. It also shows the importance of groundwater flow (flux > 10?8 m/s) on thermal recovery of the ground over other factors.  相似文献   

17.
Synchrotron-based in situ angle-dispersive X-ray diffraction experiments were conducted on a natural uvite-dominated tourmaline sample by using an external-heating diamond anvil cell at simultaneously high pressures and temperatures up to 18 GPa and 723 K, respectively. The angle-dispersive X-ray diffraction data reveal no indication of a structural phase transition over the P–T range of the current experiment in this study. The pressure–volume–temperature data were fitted by the high-temperature Birch–Murnaghan equation of state. Isothermal bulk modulus of K 0 = 96.6 (9) GPa, pressure derivative of the bulk modulus of \(K_{0}^{\prime } = 12.5 \;(4)\), thermal expansion coefficient of α 0 = 4.39 (27) × 10?5 K?1 and temperature derivative of the bulk modulus (?K/?T) P  = ?0.009 (6) GPa K?1 were obtained. The axial thermoelastic properties were also obtained with K a0 = 139 (2) GPa, \(K_{a0}^{\prime }\) = 11.5 (7) and α a0 = 1.00 (11) × 10?5 K?1 for the a-axis, and K c0 = 59 (1) GPa, \(K_{c0}^{\prime }\) = 11.4 (5) and α c0 = 2.41 (24) × 10?5 K?1 for the c-axis. Both of axial compression and thermal expansion exhibit large anisotropic behavior. Thermoelastic parameters of tourmaline in this study were also compared with that of the other two ring silicates of beryl and cordierite.  相似文献   

18.
The electrical conductivity of aqueous fluids containing 0.01, 0.1, and 1 M NaCl was measured in an externally heated diamond cell to 600 °C and 1 GPa. These measurements therefore more than double the pressure range of previous data and extend it to higher NaCl concentrations relevant for crustal and mantle fluids. Electrical conductivity was generally found to increase with pressure and fluid salinity. The conductivity increase observed upon variation of NaCl concentration from 0.1 to 1 M was smaller than from 0.01 to 0.1 M, which reflects the reduced degree of dissociation at high NaCl concentration. Measured conductivities can be reproduced (R 2 = 0.96) by a numerical model with log \(\sigma\) = ?1.7060– 93.78/T + 0.8075 log c + 3.0781 log \(\rho\) + log \(\varLambda\) 0(T, \(\rho\)), where \(\sigma\) is the conductivity in S m?1, T is temperature in K, c is NaCl concentration in wt%, \(\rho\) is the density of pure water (in g/cm3) at given pressure and temperature, and \(\varLambda\) 0 (T, \(\rho\)) is the molar conductivity of NaCl in water at infinite dilution (in S cm2 mol?1), \(\varLambda\) 0 = 1573–1212 \(\rho\) + 537 062/T–208 122 721/T 2. This model allows accurate predictions of the conductivity of saline fluids throughout most of the crust and upper mantle; it should not be used at temperatures below 100 °C. In general, the data show that already a very small fraction of NaCl-bearing aqueous fluid in the deep crust is sufficient to enhance bulk conductivities to values that would be expected for a high degree of partial melting. Accordingly, aqueous fluids may be distinguished from hydrous melts by comparing magnetotelluric and seismic data. H2O–NaCl fluids may enhance electrical conductivities in the deep crust with little disturbance of v p or v p/v s ratios. However, at the high temperatures in the mantle wedge above subduction zones, the conductivity of hydrous basaltic melts and saline aqueous fluids is rather similar, so that distinguishing these two phases from conductivity data alone is difficult. Observed conductivities in forearc regions, where temperatures are too low to allow melting, may be accounted for by not more than 1 wt% of an aqueous fluid with 5 wt% NaCl, if this fluid forms a continuous film or fills interconnected tubes.  相似文献   

19.
The thermal evolution of 10-Å phase Mg3Si4O10(OH)2·H2O, a phyllosilicate which may have an important role in the storage/release of water in subducting slabs, was studied by X-ray single-crystal diffraction in the temperature range 116–293 K. The lattice parameters were measured at several intervals both on cooling and heating. The structural model was refined with intensity data collected at 116 K and compared to the model refined at room temperature. As expected for a layer silicate on cooling in this temperature range, the a and b lattice parameters undergo a small linear decrease, α a  = 1.7(4) 10?6 K?1 and α b  = 1.9(4) 10?6 K?1, where α is the linear thermal expansion coefficient. The greater variation is along the c axis and can be modeled with the second order polynomial c T  = c 293(1 + 6.7(4)10?5 K?1ΔT + 9.5(2.5)10?8 K?2(ΔT)2) where ΔT = T ? 293 K; the monoclinic angle β slightly increased. The cell volume thermal expansion can be modeled with the polynomial V T  = V 293 (1 + 8.0 10?5 K?1 ΔT + 1.4 10?7 K?2 (ΔT)2) where ΔT = T ? 293 is in K and V in Å3. These variations were similar to those expected for a pressure increase, indicating that T and P effects are approximately inverse. The least-squares refinement with intensity data measured at 116 K shows that the volume of the SiO4 tetrahedra does not change significantly, whereas the volume of the Mg octahedra slightly decreases. To adjust for the increased misfit between the tetrahedral and octahedral sheets, the tetrahedral rotation angle α changes from 0.58° to 1.38°, increasing the ditrigonalization of the silicate sheet. This deformation has implications on the H-bonds between the water molecule and the basal oxygen atoms. Furthermore, the highly anisotropic thermal ellipsoid of the H2O oxygen indicates positional disorder, similar to the disorder observed at room temperature. The low-temperature results support the hypothesis that the disorder is static. It can be modeled with a splitting of the interlayer oxygen site with a statistical distribution of the H2O molecules into two positions, 0.6 Å apart. The resulting shortest Obas–OW distances are 2.97 Å, with a significant shortening with respect to the value at room temperature. The low-temperature behavior of the H-bond system is consistent with that hypothesized at high pressure on the basis of the Raman spectra evolution with P.  相似文献   

20.
The in situ Raman spectra of a hydrous anorthoclase at temperatures of 20–800 °C have been measured using a LABRAM-HR spectrometer and Linkam TS 1500 heating stage. The frequencies of modes at 54, 99, 130 and 162 cm?1 related to M–O vibrations decrease sharply and then increase drastically or keep steady at temperatures above 200 °C. A knee point can be clearly seen at about 200 °C for those modes. The frequency of the mode at 282 cm?1 shows little temperature dependence. However, for the two strongest modes at 471 and 512 cm?1, the frequencies decrease linearly with increasing temperature. From evolution of the frequencies of modes at 54, 99, 130 and 162 cm?1 with temperature, the following conclusions can be drawn: (1) The distance of the local M–O bond shortens rather than lengthens at temperatures above 200 °C; (2) The abrupt changes of the local structure of M site induce a collapse of the framework structure and displacive phase transition at 200 °C; and (3) The H atoms incorporated in anorthoclase are located at the M site. These results are indicative for the structure and properties of anorthoclase at deep earth conditions.  相似文献   

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