Heat capacity,entropy and phase equilibria of stishovite     

Wenjun?YongEmail author  Edgar?Dachs  Artur?Benisek  Richard?A.?Secco 《Physics and Chemistry of Minerals》2012,39(2):153-162

The low-temperature heat capacity (C _P) of stishovite (SiO₂) synthesized with a multi-anvil device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system (PPMS) and around ambient temperature using a differential scanning calorimeter (DSC). The entropy of stishovite at standard temperature and pressure calculated from DSC-corrected PPMS data is 24.94 J mol⁻¹ K⁻¹, which is considerably smaller (by 2.86 J mol⁻¹ K⁻¹) than that determined from adiabatic calorimetry (Holm et al. in Geochimica et Cosmochimica Acta 31:2289–2307, 1967) and about 4% larger than the recently reported value (Akaogi et al. in Am Mineral 96:1325–1330, 2011). The coesite–stishovite phase transition boundary calculated using the newly determined entropy value of stishovite agrees reasonably well with the previous experimental results by Zhang et al. (Phys Chem Miner 23:1–10, 1996). The calculated phase boundary of kyanite decomposition reaction is most comparable with the experimental study by Irifune et al. (Earth Planet Sci Lett 77:245–256, 1995) at low temperatures around 1,400 K, and the calculated slope in this temperature range is mostly consistent with that determined by in situ X-ray diffraction experiments (Ono et al. in Am Mineral 92:1624–1629, 2007).  相似文献   

Effect of pressure on the thermal expansion of MgO up to 8.2 GPa     

J. Zhang 《Physics and Chemistry of Minerals》2000,27(3):145-148

Isobaric volume measurements for MgO were carried out at 2.6, 5.4, and 8.2 GPa in the temperature range 300–1073 K using a DIA-type, large-volume apparatus in conjunction with synchrotron X-ray powder diffraction. Linear fit of the thermal expansion data over the experimental pressure range yields the pressure derivative, (∂α/∂P) _T , of −1.04(8) × 10⁻⁶ GPa⁻¹ K⁻¹ and the mean zero-pressure thermal expansion α_{0, T}  = 4.09(6) × 10⁻⁵ K⁻¹. The α_{0, T} value is in good agreement with results of Suzuki (1975) and Utsumi et al. (1998) over the same temperature range, whereas (∂α/∂P) _T is determined for the first time on MgO by direct measurements. The cross-derivative (∂α²/∂P∂T) cannot be resolved because of large uncertainties associated with the temperature derivative of α at all pressures. The temperature derivative of the bulk modulus, (∂K _T/∂T) _P , of −0.025(3) GPa K⁻¹, obtained from the measured (∂α/∂P) _T value, is in accord with previous findings. Received: 2 April 1999 / Revised, accepted: 22 June 1999  相似文献   

Thermal equations of state of dioctahedral micas on the join muscovite–paragonite     

P. Comodi  G. D. Gatta  P. F. Zanazzi  D. Levy  W. Crichton 《Physics and Chemistry of Minerals》2002,29(8):538-544

 Powder diffraction measurements at simultaneous high pressure and temperature on samples of 2M1 polytype of muscovite (Ms) and paragonite (Pg) were performed at the beamline ID30 of ESRF (Grenoble), using the Paris-Edinburgh cell. The bulk moduli of Ms, calculated from the least-squares fitting of V–P data on each isotherm using a second-order Birch–Murnaghan EoS, were: 57.0(6), 55.1(7), 51.1(7) and 48.9(5) GPa on the isotherms at 298, 573, 723 and 873 K, respectively. The value of (∂K _T /∂T) was −0.0146(2) GPa K⁻¹. The thermal expansion coefficient α varied from 35.7(3) × 10⁻⁶ K⁻¹ at P ambient to 20.1(3) × 10⁻⁶ K⁻¹ at P = 4 GPa [(∂α/∂P) _T = −3.9(1) × 10⁻⁶ GPa⁻¹ K⁻¹]. The corresponding values for Pg on the isotherms at 298, 723 and 823 K were: bulk moduli 59.9(5), 55.7(6) and 53.8(7) GPa, (∂K _T /∂T) −0.0109(1) GPa K⁻¹. The thermal expansion coefficient α varied from 44.1(2) × 10⁻⁶ K⁻¹ at P ambient to 32.5(2) × 10⁻⁶ K⁻¹ at P = 4 GPa [(∂α/∂P) _T = −2.9(1) × 10⁻⁶ GPa⁻¹ K⁻¹]. Thermoelastic coefficients showed that Pg is stiffer than Ms; Ms softens more rapidly than Pg upon heating; thermal expansion is greater and its variation with pressure is smaller in Pg than in Ms. Received: 28 January 2002 / Accepted: 5 April 2002  相似文献   

Elasticity of TiO2 rutile to 1800 K     

D. G. Isaak  J. D. Carnes  O. L. Anderson  H. Cynn  E. Hake 《Physics and Chemistry of Minerals》1998,26(1):31-43

The ambient pressure elastic properties of single-crystal TiO₂ rutile are reported from room temperature (RT) to 1800 K, extending by more than 1200 oK the maximum temperature for which rutile elasticity data are available. The magnitudes of the temperature derivatives decrease with increasing temperature for five of the six adiabatic elastic moduli (C _ij ). At RT, we find (units, GPa): C ₁₁=268(1); C ₃₃=484(2); C ₄₄=123.8(2); C ₆₆=190.2(5); C ₂₃=147(1); and C ₁₂=175(1). The temperature derivatives (units, GPa K⁻¹) at RT are: (∂C ₁₁/∂T) _P =−0.042(5); (∂C ₃₃/∂T) _P =−0.087(6); (∂C ₄₄/∂T) _P =−0.0187(2); (∂C ₆₆/∂T) _P =−0.067(2); (∂C ₂₃/∂T) _P =−0.025; and (∂C ₁₂/∂T) _P −0.048(5). The values for K _S (adiabatic bulk modulus) and μ (isotropic shear modulus) and their temperature derivatives are K _S =212(1) GPa; μ=113(1) GPa; (∂K _S /∂T) _P =−0.040(4) GPa K⁻¹; and (∂μ/∂T) _P =−0.018(1) GPa K⁻¹. We calculate several dimensionless parameters over a large temperature range using our new data. The unusually high values for the Anderson-Gròneisen parameters at room temperature decrease with increasing temperature. At high T, however, these parameters are still well above those for most other oxides. We also find that for TiO₂, anharmonicity, as evidenced by a non-zero value of [∂ln (K _T )/∂lnV] _T , is insignificant at high T, implying that for the TiO₂ analogue of stishovite, thermal pressure is independent of volume (or pressure). Systematic relations indicate that ∂² K _S /∂T∂P is as high as 7×10⁻⁴ K⁻¹ for rutile, whereas ∂²μ/∂T∂P is an order of magnitude less. Received: 19 September 1997 / Revised, accepted: 27 February 1998  相似文献   

P–V–T equation of state of Ca₃Al₂Si₃O₁₂ grossular garnet     

Steeve Gréaux  Yoshio Kono  Norimasa Nishiyama  Takehiro Kunimoto  Kouhei Wada  Tetsuo Irifune 《Physics and Chemistry of Minerals》2011,38(2):85-94

The thermoelastic parameters of synthetic Ca₃Al₂Si₃O₁₂ grossular garnet were examined in situ at high-pressure and high-temperature by energy dispersive X-ray diffraction, using a Kawai-type multi-anvil press apparatus coupled with synchrotron radiation. Measurements have been conducted at pressures up to 20 GPa and temperatures up to 1,650 K: this P, T range covered the entire high-P, T stability field of grossular garnet. The analysis of room temperature data yielded V _0,300 = 1,664 ± 2 ?³ and K ₀ = 166 ± 3 GPa for K^￠₀ K^{\prime}_{0} fixed to 4.0. Fitting of our P–V–T data by means of the high-temperature third order Birch–Murnaghan or the Mie–Grüneisen–Debye thermal equations of state, gives the thermoelastic parameters: (∂K _0,T /∂T) _P  = −0.019 ± 0.001 GPa K⁻¹ and α _0,T  = 2.62 ± 0.23 × 10⁻⁵ K⁻¹, or γ ₀ = 1.21 for fixed values q ₀ = 1.0 and θ ₀ = 823 (Isaak et al. Phys Chem Min19:106–120, 1992). From the comparison of fits from two different approaches, we propose to constrain the bulk modulus of grossular garnet and its pressure derivative to K _T0 = 166 GPa and K^￠_T0 K^{\prime}_{T0}  = 4.03–4.35. Present results are compared with previously determined thermoelastic properties of grossular-rich garnets.  相似文献   

High-temperature elasticity of magnesioferrite spinel     

Sytle M. Antao  Ian Jackson  Baosheng Li  Jennifer Kung  Jiuhua Chen  Ishmael Hassan  Robert C. Liebermann  John B. Parise 《Physics and Chemistry of Minerals》2007,34(5):345-350

The elastic moduli of magnesioferrite spinel, MgFe₂O₄, and their temperature dependence have been determined for the first time by ultrasonic measurements on a polycrystalline specimen. The measurements were carried out at 300 MPa and to 700°C in a gas-medium high-pressure apparatus. On heating, both the elastic bulk (K _S) and shear (G) moduli decrease linearly to 350°C. By combining with extant thermal-expansion data, the values for the room-temperature K _S and G, and their temperature derivatives are as follows: K ₀ = 176.3(7) GPa, G ₀ = 80.1(2) GPa, (∂K _S/∂T) _P = −0.032(3) GPa K⁻¹ and (∂G/∂T) _P = −0.012(1) GPa K⁻¹. Between 350 and 400°C, there are abrupt increases of 1.4% in both of the elastic moduli; these closely coincide with the magnetic Curie transition that was observed by thermal analyses at about 360°C.  相似文献   

X-ray diffraction study of magnesite at high pressure and high temperature     

J. Zhang  I. Martinez  F. Guyot  P. Gillet  S. K. Saxena 《Physics and Chemistry of Minerals》1997,24(2):122-130

 P–V–T measurements on magnesite MgCO₃ have been carried out at high pressure and high temperature up to 8.6 GPa and 1285 K, using a DIA-type, cubic-anvil apparatus (SAM-85) in conjunction with in situ synchrotron X-ray powder diffraction. Precise volumes are obtained by the use of data collected above 873 K on heating and in the entire cooling cycle to minimize non-hydrostatic stress. From these data, the equation-of-state parameters are derived from various approaches based on the Birch-Murnaghan equation of state and on the relevant thermodynamic relations. With K′₀ fixed at 4, we obtain K₀=103(1) GPa, α(K⁻¹)=3.15(17)×10⁻⁵ +2.32(28)×10⁻⁸ T, (∂K_T/∂T)_P=−0.021(2) GPaK⁻¹, (dα/∂P)_T=−1.81×10⁻⁶ GPa⁻¹K⁻¹ and (∂K_T/∂T)_V= −0.007(1) GPaK⁻¹; whereas the third-order Birch-Murnaghan equation of state with K′₀ as an adjustable parameter yields the following values: K₀=108(3) GPa, K′₀=2.33(94), α(K⁻¹)=3.08(16)×10⁻⁵+2.05(27) ×10⁻⁸ T, (∂K_T/∂T)_P=−0.017(1) GPaK⁻¹, (dα/∂P)_T= −1.41×10⁻⁶ GPa⁻¹K⁻¹ and (∂K_T/∂T)_V=−0.008(1) GPaK⁻¹. Within the investigated P–T range, thermal pressure for magnesite increases linearly with temperature and is pressure (or volume) dependent. The present measurements of room-temperature bulk modulus, of its pressure derivative, and of the extrapolated zero-pressure volumes at high temperatures, are in agreement with previous single-crystal study and ultrasonic measurements, whereas (∂K_T/∂T)_P, (∂α/∂P)_T and (∂K_T/∂T)_V are determined for the first time in this compound. Using this new equation of state, thermodynamic calculations for the reactions (1) magnesite=periclase+CO₂ and (2) magnesite+enstatite=forsterite+CO₂ are consistent with existing experimental phase equilibrium data. Received September 28, 1995/Revised, accepted May 22, 1996  相似文献   

The elastic constants of monoclinic single-crystal chrome-diopside to 1,300 K     

D.G. Isaak  I. Ohno  P.C. Lee 《Physics and Chemistry of Minerals》2006,32(10):691-699

Values of the complete adiabatic elastic tensor for single-crystal chrome-diopside (a monoclinic pyroxene mineral) are presented from 298 to 1,300 K. The data were obtained using resonant ultrasound spectroscopy (RUS). They are the first published results for the temperature T dependences of the 13 individual elastic constants C _ij of any clinopyroxene mineral. Each C _ij is appropriately described by a linear function in T throughout the range of T. Values for each (∂C _ij /∂T) _P in GPa K⁻¹ are as follows: C ₁₁, −0.0291; C ₂₂, −0.0248; C ₃₃, −0.0179; C ₄₄, −0.0103; C ₅₅, −0.0077; C ₆₆, −0.0152; C ₁₂, −0.0119; C ₁₃, −0.0064; C ₂₃, 0.0000; C ₁₅, 0.0025; C ₂₅, 0.0022; C ₃₅, −0.0046; and C ₄₆, 0.0026. Values of (∂M/∂T) _P in GPa K⁻¹, where M represents an isotropic bulk property calculated from the C _ij data, are as follows: adiabatic bulk modulus K _S , −0.0123; isothermal bulk modulus K _T , −0.0178; and shear modulus G, −0.00998. Some diopside derivatives, notably (∂K _S /∂T) _P , (∂K _T /∂T) _P , and (∂V _P /∂T) _P , where V _P is the compressional wave velocity, have smaller magnitudes than all other minerals of importance in Earth’s mantle, thus, confirming predictions from systematics studies. We find several dimensionless quantities for this monoclinic mineral have normal values compared to other mantle minerals. Further, αK _T (α is the volume coefficient of thermal expansion) for diopside is approximately independent of both T and volume V at elevated temperature, so its equation of state is accurately expressed in simplified form.  相似文献   

P-V-T equation of state of lawsonite     

I. Daniel  G. Fiquet  P. Gillet  M. W. Schmidt  M. Hanfland 《Physics and Chemistry of Minerals》1999,26(5):406-414

A pressure-volume-temperature data set has been obtained for lawsonite [CaAl₂Si₂O₇(OH)₂.H₂O], using synchrotron X-ray diffraction and an externally heated diamond anvil cell. Unit-cell volumes were measured to 9.4 GPa and 767 K by angle dispersive X-ray diffraction using imaging plates. Phase changes were not observed within this pressure-temperature range, and lawsonite compressed almost isotropically at constant temperature. The P-V-T data have been analyzed using a Birch- Murnaghan equation of state and a linear equation of state expressed as β=–1/V₀ (∂V/∂P) _T . At room temperature, the derived equation of state parameters are: K ₀=124.1 (18) GPa K'₀ set to 4) and β^–1=142.0(24) GPa, respectively. Our results are intermediate between previously reported measurements. The high-temperature data show that the incompressibility of lawsonite decreases with increasing temperature to ∼500 K and then increases above. Hence, the second order temperature derivative of the bulk modulus is taken into account in the equation of state; a fit of the volume data yields K ₀=123.9(18) GPa, (∂K/∂T)_P=–0.111(3) GPa K^–1, (∂² K/∂T ²)_P=0.28(6) 10^–3 GPa K^–2, α₀=3.1(2) 10^–5 K^–1, assuming K'₀=4. Received: 2 June 1998 / Revised, accepted: 12 Ocotber 1998  相似文献   

Uncertainties on elastic parameters and occupancy factors: how do they affect the accuracy of the calculated Gibbs energy of minerals at ( P , T ) conditions? The case of 3 T - versus 2 M ₁-phengite     

Alessandro Pavese  Valeria Diella 《Physics and Chemistry of Minerals》2007,34(9):637-645

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