Effects of cation disordering in a natural MgAl2O4 spinel observed by rectangular parallelepiped ultrasonic resonance and Raman measurements     

Hyunchae Cynn  Orson L. Anderson  Malcolm Nicol 《Pure and Applied Geophysics》1993,141(2-4):415-444

At moderate temperatures, the elastic properties of natural MgAl₂O₄ spinel differ in several significant ways from properties of synthetic spinels. Below 1000 K, the ultrasonic resonant frequencies of an ordered natural spinel change significantly after heat treatment; at higher temperatures, both types of spinels have similar resonant responses. The temperature derivatives of the elastic constants of an ordered spinel also differ from those of disordered spinels at moderate temperatures; again, at higher temperatures, both types of spinels have similar behaviors. The Raman spectra also differ below 1000 K for ordered natural and disordered spinels and are similar at higher temperatures and after cooling to ambient temperature. We associate these changes in ultrasonic resonance and Raman spectra of spinel with cation disordering at high temperature which may be quenched by cooling. We deduce estimates of the inversion parameter from the relative intensities of the two A_1g Raman modes in very good agreement with estimates made from other measurements. We find thatC ₁₁ andC ₁₂ decrease by 4 and 8%, respectively, with 20% inversion in spinel;C ₄₄ is less sensitive to cation order. These results imply that previous measurements of the adiabatic elastic constants of spinels at ambient conditions have been affected by the state of cation disorder of the specimen.  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   

Thermodynamic properties and hydrogen speciation from vibrational spectra of dense hydrous magnesium silicates     

H. Cynn  A. M. Hofmeister  P. C. Burnley  A. Navrotsky 《Physics and Chemistry of Minerals》1996,23(6):361-376

Infrared absorption measurements were taken from 100 to 5000 cm^?1 of a natural chondrodite and three dense hydrous magnesium silicates: phase A, phase B, and superhydrous phase B (shy-B). Raman spectra were also acquired from phase B and the chondrodite. Roughly half of the lattice modes are represented and our data are the first report of the low frequency modes. Comparison of our new spectra to symmetry analyses suggests that multiple sites for hydrogen exist for all the phases. The shy-B we examined crystallizes in P2₁ nm with two OH sites. Models for the density of states are constructed based on band assignments for the lattice modes and for the OH stretching vibrations. Heat capacity C_P and entropy S calculated using Kieffer's formulation should be accurate within 3% from 200 to 800 K. Model values for C_P at 298 K are 299.6 J/mol-K for chondrodite, 421.5 J/mol-K for phase A, 529.4 J/mol-K for shy-B, and 618.9 J/mol-K for phase B. Model values for S₂₉₈ ⁰ are 234.2 J/mol-K for chondrodite, 303.5 J/ mol-K for phase A, 377.9 J/mol-K for shy-B, and 473.3 J/mol-K for phase B. Debye temperatures are near 1000 K.  相似文献   

Spin state of ferric iron in MgSiO3 perovskite and its effect on elastic properties     

Krystle Catalli  Sang-Heon Shim  Vitali B. Prakapenka  Jiyong Zhao  Wolfgang Sturhahn  Paul Chow  Yuming Xiao  Haozhe Liu  Hyunchae Cynn  William J. Evans 《Earth and Planetary Science Letters》2010,289(1-2):68-75

Recent studies have indicated that a significant amount of iron in MgSiO₃ perovskite (Pv) is Fe³⁺ (Fe³⁺/ΣFe = 10–60%) due to crystal chemistry effects at high pressure (P) and that Fe³⁺ is more likely than Fe²⁺ to undergo a high-spin (HS) to low-spin (LS) transition in Pv in the mantle. We have measured synchrotron Mössbauer spectroscopy (SMS), X-ray emission spectroscopy (XES), and X-ray diffraction (XRD) of Pv with all iron in Fe³⁺ in the laser-heated diamond-anvil cell to over 100 GPa. Fe³⁺ increases the anisotropy of the Pv unit cell, whereas Fe²⁺ decreases it. In Pv synthesized above 50 GPa, Fe³⁺ enters into both the dodecahedral (A) and octahedral (B) sites approximately equally, suggesting charge coupled substitution. Combining SMS and XES, we found that the LS population in the B site gradually increases with pressure up to 50–60 GPa where all Fe³⁺ in the B site becomes LS, while Fe³⁺ in the A site remains HS to at least 136 GPa. Fe³⁺ makes Pv more compressible than Mg-endmember below 50 GPa because of the gradual spin transition in the B site together with lattice compression. The completion of the spin transition at 50–60 GPa increases bulk modulus with no associated change in density. This elasticity change can be a useful seismic probe for investigating compositional heterogeneities associated with Fe³⁺.  相似文献