Sample records for stishovite
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Raman spectrum of natural and synthetic stishovite
Hemley, R.J.; Mao, Ho-kwang; Chao, E.C.T.
1986-01-01
Raman spectra of natural and synthetic samples of stishovite have been measured with a micro-optical spectrometer system. These spectra have a pattern that is characteristic of rutile-structured oxides. The spectrum of synthetic stishovite is characterized by well-resolved bands at 231, 589, 753, and 967 cm-1, which are assigned as the B1g, Eg, A1g, and B2g fundamentals, respectively, of the first-order Raman spectrum of the ideal, ordered structure. Natural stishovite obtained from Meteor Crater, Arizona has a first-order Raman spectrum that is fully consistent with that of the synthetic material. The observed spectrum of the natural sample, however, is weaker and has bands in addition to those identified as fundamentals in the spectrum of the synthetic material. A broad band at ???475 cm-1 may be indicative of glass or contaminants derived from the extraction procedure. Alternatively, this band may arise from multiphonon scattering that is enhanced by poor crystallinity or structural disorder in the natural shocked sample. ?? 1986 Springer-Verlag.
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Experimental measurements of shock properties of stishovite
International Nuclear Information System (INIS)
Furnish, M.D.; Ito, E.
1996-01-01
We have synthesized, characterized and performed Hugoniot measurements on monolithic samples of stishovite. Synthesis was accomplished in a multianvil press with pyrophyllite gaskets and carbon heaters. The samples had densities ranging from 3.80 to 4.07Mg/m 3 , corresponding to stishovite volume fractions of 0.7 to 0.87, a range confirmed by NMR analysis. They had no significant impurities except less than 1% carbon. Samples ∼1 mm thick and 3 mm diameter were tested in reverse- and forward-ballistics modes on a two-stage light gas gun, using velocity interferometry diagnostics. Impact velocities ranged from 4.0 to 6.5 km/sec. Hugoniot stresses for the four successful tests ranged from 65 to 225GPa. At higher stresses significant uncertainties arise due to impact tilt/nonplanarity issues. Results are consistent with earlier predictions of the stishovite Hugoniot based on quartz-centered Hugoniot data, static-compression (diamond-anvil cell) data and hydrostatic multianvil cell data. Release behavior appears to be frozen. These results are remarkable in view of the small size of the samples used. copyright 1996 American Institute of Physics
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Recent research on stishovite: Hugoniot and partial release Z experiments and DFT EOS calculations.
Energy Technology Data Exchange (ETDEWEB)
Furnish, Michael D.; Shulenburger, Luke; Desjarlais, Michael; Fei, Yingwei
2018-04-01
We have conducted a series of ride-along experiments on the Z facility to ascertain the Hugoniot of silica centered in the stishovite phase over a range 0.4 - 1.0 TPa, together with partial release states produced at the interface between the sample and a fused silica window. The stishovite samples were synthesized in a large-volume multi-anvil press at 15 GPa and 1773 K, with an initial density of 4.29 gm/cc. The new Z experiments on stishovite fill in a gap between gas gun experiments and NIF experiments. The states are compared with the Hugoniots of quartz and fused silica for inferences as to EOS. They are generally consistent with Sesame 7360 predictions. Sound speed constraints from these data are discussed. The new Hugoniot data cross over the melting curve of stishovite; together with the partial-release data and predictions from density-functional theory modeling, they provide insights into the properties of solid and liquid under extreme conditions. These data are fundamentally important for understanding the interior of silicate-based super-Earths.
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Recent research on stishovite: Hugoniot and partial release Z experiments and DFT EOS calculations
Furnish, Michael; Shulenburger, Luke; Desjarlais, Michael; Fei, Yingwei
2017-06-01
We have conducted a series of ride-along experiments on the Z facility to ascertain the Hugoniot of silica centered in the stishovite phase over a range 0.4 - 1.0 TPa, together with partial release states produced at the interface between the sample and a fused silica window. The stishovite samples were synthesized in a large-volume multi-anvil press at 15 GPa and 1773 K, with an initial density of 4.29 gm/cc. The new Z experiments on stishovite fill in a gap between gas gun experiments and NIF experiments. The states are compared with the Hugoniots of quartz and fused silica for inferences as to EOS. They are generally consistent with Sesame 7360 predictions. Sound speed constraints from these data are discussed. The new Hugoniot data cross over the melting curve of stishovite, providing insight into the properties of solid and liquid under extreme conditions in conjunction with predictions from density-functional theory modeling. These data are fundamentally important for understanding the interior of silicate-based super-Earths. Sandia National Labs is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corp., for the U.S. Dept. of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
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International Nuclear Information System (INIS)
Aken, P.A. van; Sharp, T.G.; Seifert, F.
1998-01-01
The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters The mean Si-O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R∼0.172 nm and N∼5) to R∼0.167 nm and N∼4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of σ N 2 ∼83.8pm 2 as it changes from σ st 2 =51.8pm 2 for sixfold to σ qu 2 =18.4pm 2 for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours. Using the EXELFS data for amorphization, a new method is developed to derive the relative amounts of Si coordinations in high-pressure minerals with mixed coordination. For the radiation-induced amorphization process of
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van Aken, P. A.; Sharp, T. G.; Seifert, F.
The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, verified by selected area electron diffraction (SAED), produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters (Si-O bond distances, coordination numbers and Debye-Waller factors). The mean Si-O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R 0.172 nm and N 5) to R 0.167 nm and N 4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of as it changes from for sixfold to for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours that is consistent with the presence of an intermediate structural state with fivefold coordination of Si. The distribution of coordination states can be estimated by
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Spray, John G.; Boonsue, Suporn
2018-01-01
Coesite and stishovite are developed in shock veins within metaquartzites beyond a radius of 30 km from the center of the 2.02 Ga Vredefort impact structure. This work focuses on deploying analytical field emission scanning electron microscopy, electron backscattered diffraction, and Raman spectrometry to better understand the temporal and spatial relations of these silica polymorphs. α-Quartz in the host metaquartzites, away from shock veins, exhibits planar features, Brazil twins, and decorated planar deformation features, indicating a primary (bulk) shock loading of >5 < 35 GPa. Within the shock veins, coesite forms anhedral grains, ranging in size from 0.5 to 4 μm, with an average of 1.25 μm. It occurs in clasts, where it displays a distinct jigsaw texture, indicative of partial reversion to a less dense SiO2 phase, now represented by microcrystalline quartz. It is also developed in the matrix of the shock veins, where it is typically of smaller size (<1 μm). Stishovite occurs as euhedral acicular crystals, typically <0.5 μm wide and up to 15 μm in length, associated with clast-matrix or shock vein margin-matrix interfaces. In this context, the needles occur as radiating or subparallel clusters, which grow into/over both coesite and what is now microcrystalline quartz. Stishovite also occurs as more blebby, subhedral to anhedral grains in the vein matrix (typically <1 μm). We propose a model for the evolution of the veins (1) precursory frictional melting in a microfault ( 1 mm wide) generates a molten matrix containing quartz clasts. This is followed by (2) arrival of the main shock front, which shocks to 35 GPa. This generates coesite in the clasts and in the matrix. (3) On initial shock release, the coesite partly reverts to a less dense SiO2 phase, which is now represented by microcrystalline quartz. (4) With continued release, stishovite forms euhedral needle clusters at solid-liquid interfaces and as anhedral crystals in the matrix. (5) With
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International Nuclear Information System (INIS)
Mo, Shang-Di; Ching, W. Y.
2001-01-01
Ab initio calculation of the XANSE/ELNES spectra for α quartz and stishovite were carried out using a large-supercell approach that includes the electron - core - hole interaction. Excellent agreements with experimental spectra were obtained for Si - K, Si - L 2,3 , and O - K edges. The usual interpretation using orbital-resolved local density of states in the conduction band is unsatisfactory. [copyright] 2001 American Institute of Physics
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Elasticity of stishovite at high pressure
Li, Baosheng; Rigden, Sally M.; Liebermann, Robert C.
1996-08-01
The elastic-wave velocities of stishovite, the rutile-structured polymorph of SiO 2, were measured to 3 GPa at room temperature in a piston cylinder apparatus using ultrasonic interferometry on polycrystalline samples. These polycrystalline samples (2-3 mm in length and diameter) were hot-pressed at 14 GPa and 1050°C in a 2000 ton uniaxial split-sphere apparatus (USSA-2000) using fused silica rods as starting material. They were characterized as low porosity (less than 1%), single phase, fine grained, free of cracks and preferred orientation, and acoustically isotropic by using density measurement, X-ray diffraction, scanning electron microscopy, and bench-top velocity measurements. On the basis of subsequent in situ X-ray diffraction study at high P and T on peak broadening on similar specimens, it is evident that the single crystal grains within these polycrystalline aggregates are well equilibrated and that these specimens are free of residual strain. P- and S-wave velocities measured at 1 atm are within 1.5% of the Hashin-Shtrikman bounds calculated from single-crystal elastic moduli. Measured pressure derivatives of the bulk and shear moduli, K' 0 = 5.3 ± 0.1 and G' 0 = 1.8 ± 0.1, are not unusual compared with values measured for other transition zone phases such as silicate spinel and majorite garnet. Isothermal compression curves calculated with the measured values of K0 and K' 0 agree well with experimental P-V data to 16 GPa. The experimental value of dG /dP is in excellent agreement with predictions based on elasticity systematics. Theoretical models are not yet able to replicate the measured values of K' 0 and G' 0.
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Structural changes induced by lattice-electron interactions: SiO2 stishovite and FeTiO3 ilmenite.
Yamanaka, Takamitsu
2005-09-01
The bright source and highly collimated beam of synchrotron radiation offers many advantages for single-crystal structure analysis under non-ambient conditions. The structure changes induced by the lattice-electron interaction under high pressure have been investigated using a diamond anvil pressure cell. The pressure dependence of electron density distributions around atoms is elucidated by a single-crystal diffraction study using deformation electron density analysis and the maximum entropy method. In order to understand the bonding electrons under pressure, diffraction intensity measurements of FeTiO3 ilmenite and gamma-SiO2 stishovite single crystals at high pressures were made using synchrotron radiation. Both diffraction studies describe the electron density distribution including bonding electrons and provide the effective charge of the cations. In both cases the valence electrons are more localized around the cations with increasing pressure. This is consistent with molecular orbital calculations, proving that the bonding electron density becomes smaller with pressure. The thermal displacement parameters of both samples are reduced with increasing pressure.
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Mineralogy of the Hydrous Lower Mantle
Shim, S. H.; Chen, H.; Leinenweber, K. D.; Kunz, M.; Prakapenka, V.; Bechtel, H.; Liu, Z.
2017-12-01
The hydrous ringwoodite inclusions found in diamonds suggest water storage in the mantle transition zone. However, water storage in the lower mantle remains unclear. Bridgmanite and magnesiowustite appear to have very little storage capacity for water. Here, we report experimental results indicating significant changes in the lower-mantle mineralogy under the presence of water. We have synthesized Mg2SiO4 ringwoodite with 2 wt% water in multi-anvil press at 20 GPa and 1573 K at ASU. The hydrous ringwoodite sample was then loaded to diamond anvil cells with Ar or Ne as a pressure medium. We heated the pure hydrous ringwoodite samples at lower-mantle pressure using a CO2 laser heating system at ASU. We measured X-ray diffraction patterns at the GSECARS sector of the Advanced Photon Source (APS) and 12.2.2 sector of the Advanced Light Source (ALS). For the separate Pt-mixed samples, we have conducted in situ heating at the beamlines using near IR laser heating systems. We measured the infrared spectra of the heated samples at high pressure and after pressure quench at 1.4.4 sector of ALS. In the in situ experiments with hydrous ringwoodite + Pt mixture as a starting material, we found formation of stishovite together with bridgmanite and periclase during heating with a near IR laser beams at 1300-2500 K and 35-66 GPa. However, some hydrous ringwoodite still remains even after a total of 45 min of heating. In contrast, the hydrous ringwoodite samples heated without Pt by CO2 laser beams are transformed completely to bridgmanite, periclase and stishovite at 31-55 GPa and 1600-1900 K. We have detected IR active OH mode of stishovite from the samples heated at lower-mantle pressures. The unit-cell volume of stishovite measured after pressure quench is greater than that of dry stishovite by 0.3-0.6%, supporting 0.5-1 wt% of H2O in stishovite in these samples. Stishovite is a thermodynamically forbidden phase in the dry lower mantle because of the existence of periclase and
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Experimental evidence of six-fold oxygen coordination for phosphorus and XANES calculations
Energy Technology Data Exchange (ETDEWEB)
Flank, A-M; Trcera, N; Itie, J-P; Lagarde, P [Synchrotron Soleil, L' Orme des Merisiers, BP 48, 91192 Gif sur Yvette (France); Brunet, F [Laboratoire de Geologie, CNRS-ENS-UMR8538, 24 rue Lhommond, 75005 Paris (France); Irifune, T [Geodynamics Research Center, Ehime University, Matsuyama 790-8577 (Japan)
2009-11-15
Phosphorus, a group V element, has always been found so far in minerals, biological systems and synthetic compounds with an oxygen coordination number of four (i.e, PO{sub 4} groups). We demonstrate here using phosphorus K-edge XANES spectroscopy that this element can also adopt a six-fold oxygen coordination (i.e, PO{sub 6} groups). This new coordination was achieved in AlPO{sub 4} doped SiO{sub 2} stishovite synthesized at 18 GPa and 1873 K and quenched down to ambient conditions. The well-crystallized P-bearing stishovite grains (up to 100{mu}m diameter) were embedded in the back-transformation products of high pressure form of AlPO{sub 4} matrix. They were identified by elemental mapping ({mu}-XRF). {mu}-XANES spectra collected at the Si and P K edges in the Si rich region with a very low concentration of P present striking resemblance, Si itself being characteristic of pure stishovite. We can therefore infer that phosphorus in the corresponding stishovite crystal is involved in an octahedral coordination made of six oxygen atoms. First principle XANES calculations using a plane-wave density functional formalism with core-hole effects treated in a supercell approach at the P K edge for a P atom substituting an Si one in the stishovite structure confirm this assertion. This result shows that in the lower-mantle where all silicon is six-fold coordinated, phosphorus has the crystal-chemical ability to remain incorporated into silicate structures.
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Experimental evidence of six-fold oxygen coordination for phosphorus and XANES calculations
Flank, A.-M.; Trcera, N.; Brunet, F.; Itié, J.-P.; Irifune, T.; Lagarde, P.
2009-11-01
Phosphorus, a group V element, has always been found so far in minerals, biological systems and synthetic compounds with an oxygen coordination number of four (i.e, PO4 groups). We demonstrate here using phosphorus K-edge XANES spectroscopy that this element can also adopt a six-fold oxygen coordination (i.e, PO6 groups). This new coordination was achieved in AlPO4 doped SiO2 stishovite synthesized at 18 GPa and 1873 K and quenched down to ambient conditions. The well-crystallized P-bearing stishovite grains (up to 100μm diameter) were embedded in the back-transformation products of high pressure form of AlPO4 matrix. They were identified by elemental mapping (μ-XRF). μ-XANES spectra collected at the Si and P K edges in the Si rich region with a very low concentration of P present striking resemblance, Si itself being characteristic of pure stishovite. We can therefore infer that phosphorus in the corresponding stishovite crystal is involved in an octahedral coordination made of six oxygen atoms. First principle XANES calculations using a plane-wave density functional formalism with core-hole effects treated in a supercell approach at the P K edge for a P atom substituting an Si one in the stishovite structure confirm this assertion. This result shows that in the lower-mantle where all silicon is six-fold coordinated, phosphorus has the crystal-chemical ability to remain incorporated into silicate structures.
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Experimental evidence of six-fold oxygen coordination for phosphorus and XANES calculations
International Nuclear Information System (INIS)
Flank, A-M; Trcera, N; Itie, J-P; Lagarde, P; Brunet, F; Irifune, T
2009-01-01
Phosphorus, a group V element, has always been found so far in minerals, biological systems and synthetic compounds with an oxygen coordination number of four (i.e, PO 4 groups). We demonstrate here using phosphorus K-edge XANES spectroscopy that this element can also adopt a six-fold oxygen coordination (i.e, PO 6 groups). This new coordination was achieved in AlPO 4 doped SiO 2 stishovite synthesized at 18 GPa and 1873 K and quenched down to ambient conditions. The well-crystallized P-bearing stishovite grains (up to 100μm diameter) were embedded in the back-transformation products of high pressure form of AlPO 4 matrix. They were identified by elemental mapping (μ-XRF). μ-XANES spectra collected at the Si and P K edges in the Si rich region with a very low concentration of P present striking resemblance, Si itself being characteristic of pure stishovite. We can therefore infer that phosphorus in the corresponding stishovite crystal is involved in an octahedral coordination made of six oxygen atoms. First principle XANES calculations using a plane-wave density functional formalism with core-hole effects treated in a supercell approach at the P K edge for a P atom substituting an Si one in the stishovite structure confirm this assertion. This result shows that in the lower-mantle where all silicon is six-fold coordinated, phosphorus has the crystal-chemical ability to remain incorporated into silicate structures.
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Gibbs, G. V.; Cox, D. F.; Ross, N. L.
Employing first-principles methods, the docking sites for H were determined and H, Al, and vacancy defects were modeled with an infinite periodic array of super unit cells each consisting of 27 contiguous symmetry nonequivalent unit cells of the crystal structure of stishovite. A geometry optimization of the super-cell structure reproduces the observed bulk structure within the experimental error when P1 translational symmetry was assumed and an array of infinite extent was generated. A mapping of the valence electrons for the structure displays mushroom-shaped isosurfaces on the O atom, one on each side of the plane of the OSi3 triangle in the nonbonded region. An H atom, placed in a cell near the center of the super cell, was found to dock upon geometry optimization at a distance of 1.69 Å from the O atom with the OH vector oriented nearly perpendicular to the plane of the triangle such that the OH vector makes a angle of 91° with respect to [001]. However, an optimization of a super cell with an Al atom replacing Si and an H atom placed nearby in a centrally located cell resulted in an OH distance of 1.02 Å with the OH vector oriented perpendicular to [001] as observed in infrared studies. The geometry-optimized position of the H atom was found to be in close agreement with that (0.44, 0.12, 0.0) determined in an earlier study of the theoretical electron density distribution. The docking of the H atom at this site was found to be 330 kJ mol-1 more stable than a docking of the atom just off the shared OO edge of the octahedra as determined for rutile. A geometry optimization of a super cell with a missing Si generated a vacant octahedra that is 20% larger than that of the SiO6 octahedra. The valence electron density distribution displayed by the two-coordinate O atoms that coordinate the vacant octahedral site is very similar to those displayed by the bent SiOSi angles in coesite. The internal distortions induced by the defect were found to diminish rather
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Energy Technology Data Exchange (ETDEWEB)
Chen, Ting [Department of Geosciences, Stony Brook University, Stony Brook New York USA; Liebermann, Robert C. [Department of Geosciences, Stony Brook University, Stony Brook New York USA; Mineral Physics Institute, Stony Brook University, Stony Brook New York USA; Zou, Yongtao [Mineral Physics Institute, Stony Brook University, Stony Brook New York USA; State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun China; Li, Ying [Mineral Physics Institute, Stony Brook University, Stony Brook New York USA; Key Laboratory of Earthquake Prediction, Institute of Earthquake Science, China Earthquake Administration, Beijing China; Qi, Xintong [Department of Geosciences, Stony Brook University, Stony Brook New York USA; Li, Baosheng [Department of Geosciences, Stony Brook University, Stony Brook New York USA; Mineral Physics Institute, Stony Brook University, Stony Brook New York USA
2017-08-12
The compressional and shear wave velocities for coesite have been measured simultaneously up to 5.8 GPa and 1073 K by ultrasonic interferometry for the first time. The shear wave velocity decreases with pressure along all isotherms. The resulting contrasts between coesite and stishovite reach ~34% and ~45% for P and S wave velocities, respectively, and ~64% and ~75% for their impedance at mantle conditions. The large velocity and impedance contrasts across coesite-stishovite transition imply that to generate the velocity and impedance contrasts observed at the X-discontinuity, only a small amount of silica would be required. The velocity jump dependences on silica, d(lnVP)/d(SiO2) = 0.38 (wt %)-1 and d(lnVS)/d(SiO2) = 0.52 (wt %)-1, are utilized to place constraints on the amount of silica in the upper mantle and provide a geophysical approach to track mantle eclogite materials and ancient subducted oceanic slabs.
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Time-resolved diffraction of shock-released SiO2 and diaplectic glass formation
International Nuclear Information System (INIS)
Gleason, A. E.; Bolme, C. A.; Lee, H. J.; Nagler, B.
2017-01-01
Understanding how rock-forming minerals transform under shock loading is critical for modeling collisions between planetary bodies, interpreting the significance of shock features in minerals and for using them as diagnostic indicators of impact conditions, such as shock pressure. To date, our understanding of the formation processes experienced by shocked materials is based exclusively on ex situ analyses of recovered samples. Formation mechanisms and origins of commonly observed mesoscale material features, such as diaplectic (i.e., shocked) glass, remain therefore controversial and unresolvable. Here in this paper we show in situ pump-probe X-ray diffraction measurements on fused silica crystallizing to stishovite on shock compression and then converting to an amorphous phase on shock release in only 2.4 ns from 33.6 GPa. Recovered glass fragments suggest permanent densification. These observations of real-time diaplectic glass formation attest that it is a back-transformation product of stishovite with implications for revising traditional shock metamorphism stages.
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High-pressure phase relations and thermodynamic properties of CaAl 4Si 2O 11 CAS phase
Akaogi, M.; Haraguchi, M.; Yaguchi, M.; Kojitani, H.
2009-03-01
Phase relations in CaAl4Si2O11 were examined at 12-23 GPa and 1000-1800 °C by multianvil experiments. A three-phase mixture of grossular, kyanite and corundum is stable below about 13 GPa at 1000-1800 °C. At higher pressure and at temperature below about 1200 °C, a mixture of grossular, stishovite and corundum is stable, indicating the decomposition of kyanite. Above about 1200 °C, CaAl4Si2O11 CAS phase is stable at pressure higher than about 13 GPa. The triple point is placed at 14.7 GPa and 1280 °C. The equilibrium boundary of formation of CAS phase from the mixture of grossular, kyanite and corundum has a small negative slope, and that from the mixture of grossular, stishovite and corundum has a strongly negative slope, while the decomposition boundary of kyanite has a small positive slope. Enthalpies of the transitions were measured by high-temperature drop-solution calorimetry. The enthalpy of formation of CaAl4Si2O11 CAS phase from the mixture of grossular, kyanite and corundum was 139.5 ± 15.6 kJ/mol, and that from the mixture of grossular, stishovite and corundum was 94.2 ± 15.4 kJ/mol. The transition boundaries calculated using the measured enthalpy data were consistent with those determined by the high-pressure experiments. The boundaries in this study are placed about 3 GPa higher in pressure and about 200 °C lower in temperature than those by Zhai and Ito [Zhai, S., Ito, E., 2008. Phase relations of CaAl4Si2O11 at high-pressure and high-temperature with implications for subducted continental crust into the deep mantle. Phys. Earth Planet. Inter. 167, 161-167]. Combining the thermodynamic data measured in this study with those in the literature, dissociation boundary of CAS phase into a mixture of Ca-perovskite, corundum and stishovite and that of grossular into Ca-perovskite plus corundum were calculated to further constrain the stability field of CAS phase. The result suggests that the stability of CAS phase would be limited at the bottom of
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A New Multiphase Equation of State for SiO2
Energy Technology Data Exchange (ETDEWEB)
Maerzke, Katie A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Gammel, J. Tinka [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
2017-10-06
SiO2 is found as α-quartz at ambient conditions. Under shock compression, it transforms into a much higher density stishovite-like phase around 20 GPa, then into a liquid phase above 100 GPa. The SESAME library contains older equations of state for α-quartz, polycrystalline quartz, and fused quartz. These equations of state model the material as a single phase; i.e., there is no high pressure phase transition. Somewhat more recently (in 1992), Jon Boettger published equations of state for α-quartz, coesite, and stishovite, along with a phase transition model to mix them. However, we do not have a multiphase EOS that captures the phase transitions in this material. Others are working on a high-accuracy model for very high pressure SiO2, since liquid quartz is used as an impedance matching standard above 100 GPa; however, we are focused on the 10-50 GPa range. This intermediate pressure range is most relevant for modeling the decomposition products of silicone polymers such as Sylgard 184 and SX358.
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A new equation of state for α-quartz
Magyar, Rudolph; Carpenter, John
2015-06-01
Quartz (SiO2) is often used as an optically transparent window for visar signals in shock experiments and is itself an active component of the experiments. Therefore, the shock response of quartz is an important input that must be known to high fidelity for precise measurement of other materials. We describe on-going work to develop a wide-range equation of state table that includes multiple phases and incorporates the latest high quality experimental and density functional theory (DFT) calculations. The emphasis in this work is the proper description of α-quartz along its principal Hugoniot through Stishovite and liquid phases. While molecular dissociation occurs at high pressures and temperatures, we find that an additional dissociation model is unnecessary. Although SiO2 possesses a number of solid phases, we restrict our focus to α-quartz and Stishovite as these two provide the density change along the Hugoniot path. We compare the model to recently measured data on Sandia's Z-machine. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE.
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Is the X-discontinuity really related to the presence of eclogite bodies in the mantle?
Woodland, Alan; Knapp, Nadia; Klimm, Kevin
2013-04-01
A local seismic feature observed at ~300 km depth is referred to as the X-discontinuity (X-disc, e.g. Revenaugh & Jordan 1991). Several petrological explanations have been proposed for this discontinuity, but Pushcharovsky & Pushcharovsky (2012) attribute it to the formation of stishovite in eclogitic bodies, based upon the suggestion of Williams & Revenaugh (2005). If this link between the X-disc and the presence of eclogite is valid, it could have important geodynamic implications. In their model, stishovite appears in the eclogitic assemblage either through the transformation of previously existing free coesite or by exsolution of "excess" SiO2 from Ca-Eskola-bearing clinopyroxene (Ca0.50.5Si2O6). Essential to this model is if the amount of free SiO2 is enough to produce the observed seismic impedance contrast or not. To test whether exsolution of stishovite from Ca-Eskola-bearing clinopyroxene is a feasible mechanism, we have undertaken high-pressure experiments to determine the maximum Ca-Eskola component that can be incorporated in clinopyroxene over a range of P-T conditions, both shallower and deeper than that corresponding to the position of the X-disc. One series of experiments were performed in the simplified CaO-MgO-Al2O3-SiO2±Na2O system and one with 3 "natural" analog eclogite compositions (K2O-Na2O-CaO-MgO-FeO-Al2O3-SiO2). For the CMAS-experiments, all samples have the typical eclogitic assemblage of clinopyroxene + garnet ± SiO2 ± kyanite. With increasing pressure, the amount of garnet increases at the expense of clinopyroxene. Maximizing the Ca-Eskola content of clinopyroxene requires coexistence with a free SiO2 phase and an elevated Al2O3 content, but not necessarily the presence of kyanite. Ca-Eskola contents of ~20 mol % are obtained at 4 GPa, but decrease steadily with increasing pressure so that ˜ 4 mol % is present at pressures corresponding to the depth of the X-disc. Experiments in natural analog eclogite compositions produced even
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Avuthu, Vasudeva Reddy
Despite the clear benefits offered by more advanced transparent materials, (e.g. transparent ceramics offer a very attractive combination of high stiffness and high hardness levels, highly-ductile transparent polymers provide superior fragment-containing capabilities, etc.), ballistic ceramic-glass like fused-silica remains an important constituent material in a majority of transparent impact-resistant structures (e.g. windshields and windows of military vehicles, portholes in ships, ground vehicles and spacecraft) used today. Among the main reasons for the wide-scale use of glass, the following three are most frequently cited: (i) glass-structure fabrication technologies enable the production of curved, large surface-area, transparent structures with thickness approaching several inches; (ii) relatively low material and manufacturing costs; and (iii) compositional modifications, chemical strengthening, and controlled crystallization have been demonstrated to be capable of significantly improving the ballistic properties of glass. In the present work, the potential of high-pressure devitrification and densification of fused-silica as a ballistic-resistance-enhancement mechanism is investigated computationally. In the first part of the present work, all-atom molecular-level computations are carried out to infer the dynamic response and material microstructure/topology changes of fused silica subjected to ballistic impact by a nanometer-sized hard projectile. The analysis was focused on the investigation of specific aspects of the dynamic response and of the microstructural changes such as the deformation of highly sheared and densified regions, and the conversion of amorphous fused silica to SiO2 crystalline allotropic modifications (in particular, alpha-quartz and stishovite). The microstructural changes in question were determined by carrying out a post-processing atom-coordination procedure. This procedure suggested the formation of high-density stishovite (and
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Discovery of moganite in a lunar meteorite as a trace of H2O ice in the Moon’s regolith
Seto, Yusuke; Miyake, Akira; Sekine, Toshimori; Tomeoka, Kazushige; Matsumoto, Megumi; Kobayashi, Takamichi
2018-01-01
Moganite, a monoclinic SiO2 phase, has been discovered in a lunar meteorite. Silica micrograins occur as nanocrystalline aggregates of mostly moganite and occasionally coesite and stishovite in the KREEP (high potassium, rare-earth element, and phosphorus)–like gabbroic-basaltic breccia NWA 2727, although these grains are seemingly absent in other lunar meteorites. We interpret the origin of these grains as follows: alkaline water delivery to the Moon via carbonaceous chondrite collisions, fluid capture during impact-induced brecciation, moganite precipitation from the captured H2O at pH 9.5 to 10.5 and 363 to 399 K on the sunlit surface, and meteorite launch from the Moon caused by an impact at 8 to 22 GPa and >673 K. On the subsurface, this captured H2O may still remain as ice at estimated bulk content of >0.6 weight %. This indicates the possibility of the presence of abundant available water resources underneath local sites of the host bodies within the Procellarum KREEP and South Pole Aitken terranes. PMID:29732406
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Effect of a core-softened O-O interatomic interaction on the shock compression of fused silica
Izvekov, Sergei; Weingarten, N. Scott; Byrd, Edward F. C.
2018-03-01
Isotropic soft-core potentials have attracted considerable attention due to their ability to reproduce thermodynamic, dynamic, and structural anomalies observed in tetrahedral network-forming compounds such as water and silica. The aim of the present work is to assess the relevance of effective core-softening pertinent to the oxygen-oxygen interaction in silica to the thermodynamics and phase change mechanisms that occur in shock compressed fused silica. We utilize the MD simulation method with a recently published numerical interatomic potential derived from an ab initio MD simulation of liquid silica via force-matching. The resulting potential indicates an effective shoulder-like core-softening of the oxygen-oxygen repulsion. To better understand the role of the core-softening we analyze two derivative force-matching potentials in which the soft-core is replaced with a repulsive core either in the three-body potential term or in all the potential terms. Our analysis is further augmented by a comparison with several popular empirical models for silica that lack an explicit core-softening. The first outstanding feature of shock compressed glass reproduced with the soft-core models but not with the other models is that the shock compression values at pressures above 20 GPa are larger than those observed under hydrostatic compression (an anomalous shock Hugoniot densification). Our calculations indicate the occurrence of a phase transformation along the shock Hugoniot that we link to the O-O repulsion core-softening. The phase transformation is associated with a Hugoniot temperature reversal similar to that observed experimentally. With the soft-core models, the phase change is an isostructural transformation between amorphous polymorphs with no associated melting event. We further examine the nature of the structural transformation by comparing it to the Hugoniot calculations for stishovite. For stishovite, the Hugoniot exhibits temperature reversal and associated
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Reduced sediment melting at 7.5-12 GPa: phase relations, geochemical signals and diamond nucleation
Brey, G. P.; Girnis, A. V.; Bulatov, V. K.; Höfer, H. E.; Gerdes, A.; Woodland, A. B.
2015-08-01
Melting of carbonated sediment in the presence of graphite or diamond was experimentally investigated at 7.5-12 GPa and 800-1600 °C in a multianvil apparatus. Two starting materials similar to GLOSS of Plank and Langmuir (Chem Geol 145:325-394, 1998) were prepared from oxides, carbonates, hydroxides and graphite. One mixture (Na-gloss) was identical in major element composition to GLOSS, and the other was poorer in Na and richer in K (K-gloss). Both starting mixtures contained ~6 wt% CO2 and 7 wt% H2O and were doped at a ~100 ppm level with a number of trace elements, including REE, LILE and HFSE. The near-solidus mineral assemblage contained a silica polymorph (coesite or stishovite), garnet, kyanite, clinopyroxene, carbonates (aragonite and magnesite-siderite solid solution), zircon, rutile, bearthite and hydrous phases (phengite and lawsonite at 10 GPa). Hydrous phases disappear at ~900 °C, and carbonates persist up to 1000-1100 °C. At temperatures >1200 °C, the mineral assemblage consists of coesite or stishovite, kyanite and garnet. Clinopyroxene stability depends strongly on the Na content in the starting mixture; it remains in the Na-gloss composition up to 1600 °C at 12 GPa, but was not observed in K-gloss experiments above 1200 °C. The composition of melt or fluid changes gradually with increasing temperature from hydrous carbonate-rich ( 1). Aragonite and Fe-Mg carbonate have very different REE partition coefficients ( D Mst-Sd/L ~ 0.01 and D Arg/L ~ 1). Nb, Ta, Zr and Hf are strongly incompatible in both carbonates. The bearthite/melt partition coefficients are very high for LREE (>10) and decrease to ~1 for HREE. All HFSE are strongly incompatible in bearthite. In contrast, Ta, Nb, Zr and Hf are moderately to strongly compatible in ZrSiO4 and TiO2 phases. Based on the obtained partition coefficients, the composition of a mobile phase derived by sediment melting in deep subduction zones was calculated. This phase is strongly enriched in
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Continuous Sound Velocity Measurements along the Shock Hugoniot Curve of Quartz
Li, Mu; Zhang, Shuai; Zhang, Hongping; Zhang, Gongmu; Wang, Feng; Zhao, Jianheng; Sun, Chengwei; Jeanloz, Raymond
2018-05-01
We report continuous measurements of the sound velocity along the principal Hugoniot curve of α quartz between 0.25 and 1.45 TPa, as determined from lateral release waves intersecting the shock front as a function of time in decaying-shock experiments. The measured sound velocities are lower than predicted by prior models, based on the properties of stishovite at densities below ˜7 g /cm3 , but agree with density functional theory molecular dynamics calculations and an empirical wide-regime equation of state presented here. The Grüneisen parameter calculated from the sound velocity decreases from γ ˜1 .3 at 0.25 TPa to 0.66 at 1.45 TPa. In combination with evidence for increased (configurational) specific heat and decreased bulk modulus, the values of γ suggest a high thermal expansion coefficient at ˜0. 25 - 0 .65 TPa , where SiO2 is thought to be a bonded liquid. From our measurements, dissociation of the molecular bonds persists to ˜0. 65 - 1 .0 TPa , consistent with estimates by other methods. At higher densities, the sound velocity is close to predictions from previous models, and the Grüneisen parameter approaches the ideal gas value.
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Hamers, Maartje F.; Pennock, Gill M.; Herwegh, Marco; Drury, Martyn R.
2016-10-01
Planar deformation features (PDFs) in quartz are one of the most reliable and most widely used forms of evidence for hypervelocity impact. PDFs can be identified in scanning electron microscope cathodoluminescence (SEM-CL) images, but not all PDFs show the same CL behavior: there are nonluminescent and red luminescent PDFs. This study aims to explain the origin of the different CL emissions in PDFs. Focused ion beam (FIB) thin foils were prepared of specific sample locations selected in composite color SEM-CL images and were analyzed in a transmission electron microscope (TEM). The FIB preparation technique allowed a direct, often one-to-one correlation between the CL images and the defect structure observed in TEM. This correlation shows that composite color SEM-CL imaging allows distinction between amorphous PDFs on one hand and healed PDFs and basal Brazil twins on the other: nonluminescent PDFs are amorphous, while healed PDFs and basal Brazil twins are red luminescent, with a dominant emission peak at 650 nm. We suggest that the red luminescence is the result of preferential beam damage along dislocations, fluid inclusions, and twin boundaries. Furthermore, a high-pressure phase (possibly stishovite) in PDFs can be detected in color SEM-CL images by its blue luminescence.
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Mineralogical characterization of a meteorite impact in Carancas, Puno
International Nuclear Information System (INIS)
Ceron Loayza, Maria L.; Bravo Cabrejos, Jorge A.
2009-01-01
We report the results of the study of a meteorite that impacted an inhabited zone in the neighborhood of the town of Carancas, Puno Region, about 1,300 km south of Lima. The analysis carried out by X ray diffractometry, transmission Moessbauer spectroscopy (at room temperature and at 4,2 K), and by energy dispersive X ray fluorescence reveal the presence in the meteorite simple of magnetic sites assigned to the Fe-Ni and troilite (Fe,S) phases, and of 3 paramagnetic doublets, two of them assigned to Fe 2+ , one associated to olivine and the other to pyroxene, and the third one due to a site occupied by Fe 3+ , which can be associated to oxides in a superparamagnetic state and/or by an Fe hydroxide. The soil samples from the crater reveal a composition that consists mainly of quartz, albite and impactites such as coesite and stishovite (SiO 2 ). The occurrence of these phases with a high content of SiO 2 in the crater soils strengthens the hypothesis of their origin induced by impact; we observe also the presence of the Fe oxide hematite, of aluminum silicates such as illite and montmorillonite, and an unassigned phase of Fe 3+ . In general, the results obtained by these techniques complement each other rather well and allow the verification of the origin of the studied simples. (author).
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Deep-Earth Equilibration between Molten Iron and Solid Silicates
Brennan, M.; Zurkowski, C. C.; Chidester, B.; Campbell, A.
2017-12-01
Elemental partitioning between iron-rich metals and silicate minerals influences the properties of Earth's deep interior, and is ultimately responsible for the nature of the core-mantle boundary. These interactions between molten iron and solid silicates were influential during planetary accretion, and persist today between the mantle and liquid outer core. Here we report the results of diamond anvil cell experiments at lower mantle conditions (40 GPa, >2500 K) aimed at examining systems containing a mixture of metals (iron or Fe-16Si alloy) and silicates (peridotite). The experiments were conducted at pressure-temperature conditions above the metallic liquidus but below the silicate solidus, and the recovered samples were analyzed by FIB/SEM with EDS to record the compositions of the coexisting phases. Each sample formed a three-phase equilibrium between bridgmanite, Fe-rich metallic melt, and an oxide. In one experiment, using pure Fe, the quenched metal contained 6 weight percent O, and the coexisting oxide was ferropericlase. The second experiment, using Fe-Si alloy, was highly reducing; its metal contained 10 wt% Si, and the coexisting mineral was stishovite. The distinct mineralogies of the two experiments derived from their different starting metals. These results imply that metallic composition is an important factor in determining the products of mixed phase iron-silicate reactions. The properties of deep-Earth interfaces such as the core-mantle boundary could be strongly affected by their metallic components.
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Energy Technology Data Exchange (ETDEWEB)
S Jacobsen; Z Liu; T Boffa Ballaran; E Littlefield; L Ehm; R Hemley
2011-12-31
The mantle X-discontinuity, usually assigned to positive seismic velocity reflectors in the 260-330 km depth range, has proved difficult to explain in terms of a single mineralogical phase transformation in part because of its depth variability. The coesite to stishovite transition of SiO{sub 2} matches deeper X-discontinuity depths but requires 5-10% free silica in the mantle to match observed impedance contrast. The orthoenstatite (OEn) to high-pressure clinoenstatite (HPCen) transformation of MgSiO{sub 3} also broadly coincides with depths of the X but requires chemically depleted and orthoenstatite-rich lithology at 300 km depth in order to match observed seismic impedance contrast. On the basis of high-pressure infrared spectroscopy, X-ray diffraction, and Raman spectroscopy, we show that 1300 ppm variation of H{sub 2}O content in MgSiO{sub 3} can displace the transition of low-pressure clinoenstatite (LPCen) to HPCen by up to 2 GPa, similar to previous quench experiments on the OEn to HPCen phase transition, where about 30-45 km (1.0-1.5 GPa) of deflection could occur per 0.1 wt% H{sub 2}O. If the mantle X-discontinuity results from pyroxene transitions in a depleted harzburgite layer, because of the strong influence of minor amounts of water on the transformation boundary, the depth of the mantle X-discontinuity could serve as a potentially sensitive indicator of water content in the uppermantle.
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Crystal chemistry of six-coordinated silicon: A key to understanding the earth's deep interior
International Nuclear Information System (INIS)
Finger, L.W.; Hazen, R.M.
1991-01-01
A survey of high-pressure silicates reveals 12 distinct high-density structural topologies with octahedral Si. Seven of these structure types - stishovite, perovskite, ilmenite, hollandite, calcium ferrite, pyrochlore and K 2 NiF 4 type - contain only six-corrdinated silicon. Other high-pressure silicates, including those with the garnet, pyroxene, wadeite, anhydrous phase B and phase B structures, contain both tetrahedral and octahedral Si. Five systematic trends among these dozen structures suggest the existence of other, as yet unobserved, possible mantle Si phases. The criteria are: (1) Structures like rutile, hollandite and calcium ferrite formed from edge-sharing chains of silicon octahedra; (2) germanates synthesized at room pressure with octahedral Ge; (3) isomorphs of room-pressure oxides with 3+ or 4+ transition-metal cations; (4) high-pressure magnesium silicates related to room-pressure aluminates by the substitution 2Al→Mg+Si; and (5) the homologous structures in system Mg-Si-O-H that includes phase B and anhydrous phase B. Each of these criteria can be used to predict other potential octahedral Si phases. Of special interest are predicted structure types that fulfill more than one criterion: Diaspore-type (MgSi)O 2 (OH) 2 , aerugite-type Mg 10 Si 3 O 16 , sphene-type CaSi 2 O 5 , benitoite-type BaSi 4 O 9 , gibbsite-type MgSi(OH) 6 and pseudobrookite-type Fe 2 SiO 5 . (orig.)
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Driver, K. P.; Cohen, R. E.; Wu, Z.; Militzer, B.; Ríos, P. L.; Towler, M. D.; Needs, R. J.; Wilkins, J. W.
2011-12-01
Silica (SiO2) is an abundant component of the Earth whose crystalline polymorphs play key roles in its structure and dynamics. First principle density functional theory (DFT) methods have often been used to accurately predict properties of silicates, but fundamental failures occur. Such failures occur even in silica, the simplest silicate, and understanding pure silica is a prerequisite to understanding the rocky part of the Earth. Here, we study silica with quantum Monte Carlo (QMC), which until now was not computationally possible for such complex materials, and find that QMC overcomes the failures of DFT. QMC is a benchmark method that does not rely on density functionals but rather explicitly treats the electrons and their interactions via a stochastic solution of Schrödinger's equation. Using ground-state QMC plus phonons within the quasiharmonic approximation of density functional perturbation theory, we obtain the thermal pressure and equations of state of silica phases up to Earth's core-mantle boundary. Our results provide the best constrained equations of state and phase boundaries available for silica. QMC indicates a transition to the dense α-PbO2 structure above the core-insulating D" layer, but the absence of a seismic signature suggests the transition does not contribute significantly to global seismic discontinuities in the lower mantle. However, the transition could still provide seismic signals from deeply subducted oceanic crust. We also find an accurate shear elastic constant for stishovite and its geophysically important softening with pressure.
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Silicon Monoxide at 1 atm and Elevated Pressures: Crystalline or Amorphous?
AlKaabi, Khalid
2014-03-05
The absence of a crystalline SiO phase under ordinary conditions is an anomaly in the sequence of group 14 monoxides. We explore theoretically ordered ground-state and amorphous structures for SiO at P = 1 atm, and crystalline phases also at pressures up to 200 GPa. Several competitive ground-state P = 1 atm structures are found, perforce with Si-Si bonds, and possessing Si-O-Si bridges similar to those in silica (SiO2) polymorphs. The most stable of these static structures is enthalpically just a little more stable than a calculated random bond model of amorphous SiO. In that model we find no segregation into regions of amorphous Si and amorphous SiO2. The P = 1 atm structures are all semiconducting. As the pressure is increased, intriguing new crystalline structures evolve, incorporating Si triangular nets or strips and stishovite-like regions. A heat of formation of crystalline SiO is computed; it is found to be the most negative of all the group 14 monoxides. Yet, given the stability of SiO2, the disproportionation 2SiO (s) → Si(s)+SiO2(s) is exothermic, falling right into the series of group 14 monoxides, and ranging from a highly negative ΔH of disproportionation for CO to highly positive for PbO. There is no major change in the heat of disproportionation with pressure, i.e., no range of stability of SiO with respect to SiO2. The high-pressure SiO phases are metallic. © 2014 American Chemical Society.
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Cavosie, Aaron; Timms, Nicholas E.; Erickson, Timmons M.; Hagerty, Justin J.; Hörz, Friedrich
2016-01-01
Granular zircon in impact environments has long been recognized but remains poorly understood due to lack of experimental data to identify mechanisms involved in its genesis. Meteor Crater in Arizona (United States) contains abundant evidence of shock metamorphism, including shocked quartz, the high pressure polymorphs coesite and stishovite, diaplectic SiO2 glass, and lechatelierite (fused SiO2). Here we report the presence of granular zircon, a new shocked mineral discovery at Meteor Crater, that preserve critical orientation evidence of specific transformations that occurred during its formation at extreme impact conditions. The zircon grains occur as aggregates of sub-µm neoblasts in highly shocked Coconino Formation Sandstone (CFS) comprised of lechatelierite. Electron backscatter diffraction shows that each grain consists of multiple domains, some with boundaries disoriented by 65°, a known {112} shock-twin orientation. Other domains have crystallographic c-axes in alignment with {110} of neighboring domains, consistent with the former presence of the high pressure ZrSiO4 polymorph reidite. Additionally, nearly all zircon preserve ZrO2 + SiO2, providing evidence of partial dissociation. The genesis of CFS granular zircon started with detrital zircon that experienced shock-twinning and reidite formation from 20 to 30 GPa, ultimately yielding a phase that retained crystallographic memory; this phase subsequently recrystallized to systematically oriented zircon neoblasts, and in some areas partially dissociated to ZrO2. The lechatelierite matrix, experimentally constrained to form at >2000 °C, provided an ultra high-temperature environment for zircon dissociation (~1670 °C) and neoblast formation. The capacity of granular zircon to preserve a cumulative P-T record has not been recognized previously, and provides a new method for retrieving histories of impact-related mineral transformations in the crust at conditions far beyond which most rocks melt.
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Dynamism or Disorder at High Pressures?
Angel, R. J.; Bismayer, U.; Marshall, W. G.
2002-12-01
Phase transitions in minerals at elevated temperatures typically involve dynamics as a natural consequence of the increase in thermal energy available to the system. Classic examples include quartz, cristobalite, and carbonates in which the high-temperature, high symmetry phase is dynamically disordered. This disorder has important thermodynamic consequences, including displacement and curvature of phase boundaries (e.g. calcite-aragonite). In other minerals such as clinopyroxenes and anorthite feldspar, the dynamic behaviour is restricted to the neighbourhood of the phase transition. The fundamental question is whether increasing pressure generally suppresses such dynamic behaviour (as in anorthite; Angel, 1988), or not. In the latter case it must be included in thermodynamic models of high-pressure phase equilibria and seismological modelling of the mantle; the potential dynamics and softening in stishovite may provide the critical observational constraint on the presence or otherwise of free silica in the lower mantle. We have continued to use the lead phosphate as a prototype ferroelastic in which to understand dynamic behaviour, simply because its dynamics and transition behaviour is far better characterised than any mineral. Furthermore, the phase transition is at a pressure where experimental difficulties do not dominate the experimental results. Our previous neutron diffraction study (Angel et al., 2001) revealed that some disorder, either dynamic or static, is retained in the high-symmetry, high-pressure phase just above the phase transition. New neutron diffraction data on the pure material now suggests that this disorder slowly decreases with increasing pressure until at twice the transition pressure it is ordered. Further data for doped material provides insights into the nature of this disorder. Angel (1988) Amer. Mineral. 73:1114. Angel et al (2001) J PhysC 13: 5353.
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The effect of a realistic thermal diffusivity on numerical model of a subducting slab
Maierova, P.; Steinle-Neumann, G.; Cadek, O.
2010-12-01
A number of numerical studies of subducting slab assume simplified (constant or only depth-dependent) models of thermal conductivity. The available mineral physics data indicate, however, that thermal diffusivity is strongly temperature- and pressure-dependent and may also vary among different mantle materials. In the present study, we examine the influence of realistic thermal properties of mantle materials on the thermal state of the upper mantle and the dynamics of subducting slabs. On the basis of the data published in mineral physics literature we compile analytical relationships that approximate the pressure and temperature dependence of thermal diffusivity for major mineral phases of the mantle (olivine, wadsleyite, ringwoodite, garnet, clinopyroxenes, stishovite and perovskite). We propose a simplified composition of mineral assemblages predominating in the subducting slab and the surrounding mantle (pyrolite, mid-ocean ridge basalt, harzburgite) and we estimate their thermal diffusivity using the Hashin-Shtrikman bounds. The resulting complex formula for the diffusivity of each aggregate is then approximated by a simpler analytical relationship that is used in our numerical model as an input parameter. For the numerical modeling we use the Elmer software (open source finite element software for multiphysical problems, see http://www.csc.fi/english/pages/elmer). We set up a 2D Cartesian thermo-mechanical steady-state model of a subducting slab. The model is partly kinematic as the flow is driven by a boundary condition on velocity that is prescribed on the top of the subducting lithospheric plate. Reology of the material is non-linear and is coupled with the thermal equation. Using the realistic relationship for thermal diffusivity of mantle materials, we compute the thermal and flow fields for different input velocity and age of the subducting plate and we compare the results against the models assuming a constant thermal diffusivity. The importance of the
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Nagel, Thorsten; Düsterhöft, Erik; Schiffer, Christian
2017-04-01
We investigate the signature relevant mantle lithologies leave in the receiver function record for different adiabatic thermal gradients down to 800 kilometers depth. The parameter space is chosen to target the visibility of upwelling mantle (a plume). Seismic velocities for depleted mantle, primitive mantle, and three pyroxenites are extracted from thermodynamically calculated phases diagrams, which also provide the adiabatic decompression paths. Results suggest that compositional variations, i.e. the presence or absence of considerable amounts of pyroxenites in primitive mantle should produce a clear footprint while horizontal differences in thermal gradients for similar compositions might be more subtle. Peridotites best record the classic discontinuities at around 410 and 650 kilometers depth, which are associated with the olivin-wadsleyite and ringwoodite-perovskite transitions, respectively. Pyroxenites, instead, show the garnet-perovskite transition below 700 kilometers depth and SiO2-supersaturated compositions like MORB display the coesite-stishovite transition between 300 and 340 kilometers depth. The latter shows the strongest temperature-depth dependency of all significant transitions potentially allowing to infer information about the thermal state if the mantle contains a sufficient fraction of MORB-like compositions. For primitive and depleted mantle compositions, the olivin-wadsleyite transition shows a certain temperature-depth dependency reflected in slightly larger delay times for higher thermal gradients. The lower-upper-mantle discontinuity, however, is predicted to display larger delay times for higher thermal gradients although the associated assemblage transition occurs at shallower depths thus requiring a very careful depth migration if a thermal anomaly should be recognized. This counterintuitive behavior results from the downward replacement of the assemblage wadsleyite+garnet with the assemblage garnet+periclase at high temperatures
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Seismic scatterers in the mid-lower mantle beneath Tonga-Fiji
Kaneshima, Satoshi
2018-01-01
We analyze deep and intermediate-depth earthquakes at the Tonga-Fiji region in order to reveal the distribution of scattering objects in the mid-lower mantle. By array processing waveform data recorded at regional seismograph stations in the US, Alaska, and Japan, we investigate S-to-P scattering waves in the P coda, which arise from kilometer-scale chemically distinct objects in the mid-lower mantle beneath Tonga-Fiji. With ten scatterers previously reported by the author included, twenty-three mid-lower mantle scatterers have been detected below 900 km depth, while scatterers deeper than 1900 km have not been identified. Strong mid-lower mantle S-to-P scattering most frequently occurs at the scatterers located within a depth range between 1400 km and 1600 km. The number of scatterers decreases below 1600 km depth, and the deeper objects tend to be weaker. The scatterer distribution may reflect diminishing elastic anomalies of basaltic rocks with depth relative to the surrounding mantle rocks, which mineral physics has predicted to occur. The predominant occurrence of strong S-to-P scattering waves within a narrow depth range may reflect significant reduction of rigidity due to the ferro-elastic transformation of stishovite in basaltic rocks. Very large signals associated with mid-mantle scatterers are observed only for a small portion of the entire earthquake-array pairs. Such infrequent observations of large scattering signals, combined with quite large event-to-event differences in the scattering intensity for each scatterer, suggest both that the strong arrivals approximately represent ray theoretical S-to-P converted waves at objects with a plane geometry. The plane portions of the strong scatterers may often dip steeply, with the size exceeding 100 km. For a few strong scatterers, the range of receivers showing clear scattered waves varies substantially from earthquake-array pair to pair. Some of the scatterers are also observed at different arrays that have
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Anelasticity maps for acoustic dissipation associated with phase transitions in minerals
Carpenter, Michael A.; Zhang, Zhiying
2011-07-01
Acoustic dissipation due to structural phase transitions in minerals could give rise to large seismic attenuation effects superimposed on the high temperature background contribution from dislocations and grain boundaries in the Earth. In addition to the possibility of a sharp peak actually at a transition point for both compressional and shear waves, significant attenuation might arise over wider temperature intervals due to the mobility of transformation twins or other defects associated with the transition. Attenuation due to structural phase transitions in quartz, pyroxenes, perovskites, stishovite and hollandite, or to spin state transitions of Fe2+ in magnesiowüstite and perovskite and the hcp/bcc transition in iron-nickel (Fe-Ni) alloy, are reviewed from this perspective. To these can be added possible loss behaviour associated with reconstructive transitions which might occur by a ledge mechanism on topotactic interfaces (orthopyroxene/clinopyroxene, olivine/spinel and perovskite/postperovskite), with impurities (Snoek effect) or with mobility of protons. There are experimental difficulties associated with measuring dissipation effects in situ at simultaneous high pressures and temperatures, so reliance is currently placed on investigation of analogue phases such as LaCoO3 for spin-state behaviour and LaAlO3 for the dynamics of ferroelastic twin walls. Similarly, it is not possible to measure loss dynamics simultaneously at the low stresses and low frequencies that pertain in seismic waves, so reliance must be placed on combining different techniques, such as dynamic mechanical analysis (low frequency, relatively high stress) and resonant ultrasound spectroscopy (high frequency, low stress), to extrapolate acoustic loss behaviour over wide frequency, temperature and stress intervals. In this context 'anelasticity maps' provide a convenient means of representing different loss mechanisms. Contouring of the inverse mechanical quality factor, Q-1, can be
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Rapp, R. P.; Nishiyama, N.; Irifune, T.; Inoue, T.; Yamasaki, D.
2003-12-01
Ocean island basalts (OIBs) provide geochemical evidence for the presence of crustally-derived sedimentary material in the deep mantle plume source region for EM-type OIBs, and global seismic tomography provides us with dramatic images of subducted slabs, presumably carrying a sediment component, penetrating through the transition zone and into the lower mantle, in some cases to the core-mantle boundary. In an effort to better constrain the geochemical effects of deeply recycled sedimentary material in subduction zones, and their role in the petrogenesis of EM-type OIBs, we have undertaken a series of phase equlibria experiments in the multi-anvil apparatus at 10-25 GPa, using natural sediment lithologies as starting materials. The goal of these experiments is to identify the dominant phases in deeply subducted sediments, constrain their P-T stability limits, and to assess their role in crustal recycling and element redistribution in the deep mantle during subduction. The phase equilibria experiments were performed in a 2000-ton Kawai-type apparatus, using tungsten carbide cubes with 3 mm TEL and Cr-doped MgO and zirconia pressure media. A cylindrical lanthanum chromite heater was used, along with short (gold capsules to minimize thermal gradients and to retain the small amounts of water (< 1 wt%) present in the starting material, and long run-durations (12-48 hours) in order to facilitate future analyses of the dominant phases for key trace elements using the ion microprobe. Our preliminary results at 10-25 GPa indicate that K-hollandite (KalSi3O3) and stishovite are the primary high-pressure phases in the sediment composition, with subordinate garnet and an as-yet-unidentified (possibly hydrous) Al-silicate phase present as well. These results suggest that K-hollandite is the primary repository for incompatible elements (e.g., La, Ce, Sr, Ba, Rb, etc., and the heat-producing elements K, U and Th) in sedimentary material recycled into the deep mantle via
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First-Principles Investigations of Defects in Minerals
Verma, Ashok K.
2011-07-01
The ideal crystal has an infinite 3-dimensional repetition of identical units which may be atoms or molecules. But real crystals are limited in size and they have disorder in stacking which as called defects. Basically three types of defects exist in solids: 1) point defects, 2) line defects, and 3) surface defects. Common point defects are vacant lattice sites, interstitial atoms and impurities and these are known to influence strongly many solid-state transport properties such as diffusion, electrical conduction, creep, etc. In thermal equilibrium point defects concentrations are determined by their formation enthalpies and their movement by their migration barriers. Line and surface defects are though absent from the ideal crystal in thermal equilibrium due to higher energy costs but they are invariably present in all real crystals. Line defects include edge-, screw- and mixed-dislocations and their presence is essential in explaining the mechanical strength and deformation of real crystals. Surface defects may arise at the boundary between two grains, or small crystals, within a larger crystal. A wide variety of grain boundaries can form in a polycrystal depending on factors such growth conditions and thermal treatment. In this talk we will present our first-principles density functional theory based defect studies of SiO2 polymorphs (stishovite, CaCl2-, α-PbO2-, and pyrite-type), Mg2SiO4 polymorphs (forsterite, wadsleyite and ringwoodite) and MgO [1-3]. Briefly, several native point defects including vacancies, interstitials, and their complexes were studied in silica polymorphs upto 200 GPa. Their values increase by a factor of 2 over the entire pressure range studied with large differences in some cases between different phases. The Schottky defects are energetically most favorable at zero pressure whereas O-Frenkel pairs become systematically more favorable at pressures higher than 20 GPa. The geometric and electronic structures of defects and migrating
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Plate tectonics hiati as the cause of global glaciations: 2. The late Proterozoic 'Snowball Earth'
Osmaston, M. F.
2003-04-01
buoyant plates. But its action is not indefinitely self-sustaining, so could die out if not "nudged" occasionally. Wholly untrumpeted by seismologists, this built-in ocean-plate-heat is indeed evident as slab-reheating during active subduction. Nearly 100 circum-Pacific tomographic transects kindly provided by E.R.Engdahl consistently show the "slab" high-Vp signature peters out at between 200 and 350 km (plate age-dependent and even at 130 Ma) and a second high-Vp signature then begins close to the top of the TZ and goes on into the lower mantle. This latter signature must be mineralogical, not thermal, and arguably is not mantle but is only a stream of dense stishovitic lumps derived from the TZ-depth partial melting of subducted oceanic crust. Where now is the slab-pull to sustain plate tectonics?
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Stability range and decomposition of potassic richterite and phlogopite end members at 5-15 GPa
International Nuclear Information System (INIS)
Troennes, R.G.
2002-01-01
The phase relations of K-richterite, KNaCaMg 5 Si 8 O 22 (OH) 2 , and phlogopite, K 3 Mg 6 Al 2 Si O20 (OH) 2 , have been investigated at pressures of 5-15 GPa and temperatures of 1000-1500 o C. K-richterite is stable to about 1450 o C at 9-10 GPa, where the dp/dT-slope of the decomposition curve changes from positive to negative. At 1000 o C the alkali-rich, low-Al amphibole is stable to more than 14 GPa. Phlogopite has a more limited stability range with a maximum thermal stability limit of 1350 o C at 4-5 GPa and a pressure stability limit of 9-10 GPa at 1000 o C. The high-pressure decomposition reactions for both of the phases produce relatively small amounts of highly alkaline water-dominated fluids, in combination with mineral assemblages that are relatively close to the decomposing hydrous phase in bulk composition. In contrast, the incongruent melting of K-richterite and phlogopite in the 1-3 GPa range involves a larger proportion of hydrous silicate melts. The K-richterite breakdown produces high-Ca pyroxene and orthoenstatite or clinoenstatite at all pressures above 4 GPa. At higher pressures additional phases are: wadeite-structured K 2 Si VI Si IV 3 O 9 at 10 GPa and 1500 o C, wadeite-structured K 2 Si VI Si IV 3 O 9 and phase X at 15 GPa and 1500 o C, and stishovite at 15 GPa and 1100 o C. The solid breakdown phases of phlogopite are dominated by pyrope and forsterite. At 9-10 GPa and 1100-1400 o C phase X is an additional phase, partly accompanied by clinoenstatite close to the decomposition curve. Phase X has variable composition. In the KCMSH-system (K 2 CaMg 5 Si 8 O 22 (OH) 2 ) investigated by Inoue et al. (1998) and in the KMASH-system investigated in this report the compositions are approximately K 4 Mg 8 Si 8 O 25 (OH) 2 and K 3.7 Mg 7.4 Al 0.6 Si 8.0 O 25 (OH) 2 , respectively. Observations from natural compositions and from the phlogopite-diopside system indicate that phlogopite-clinopyroxene assemblages are stable along common geothermal
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Mineralogy of subducted clay and clay restite in the lower mantle
Armstrong, L.; Skora, S. E.; Walter, M. J.
2012-12-01
Seismic tomography indicates that subducting oceanic lithosphere often penetrates the transition zone and eventually the lower mantle [e.g. 1, 2]. While mineralogical changes in the mafic and ultramafic portions of slabs have been well documented experimentally, the phase relations of overlying sediments at pressures above 25 GPa remain poorly studied. This is in part because sediments are expected to partially melt at sub-arc depth (P~2.5-4.5 GPa), and contribute to the genesis of arc magmas. Sediment restites left behind after the extraction of low pressure melts undergo major chemical changes, according to the melting reaction: Coe+Phen+Cpx+H2O = Grt+Ky+Melt [3]. However, sediments may not always melt depending on the thermal regime and volatile availability and composition [3]. Hence, chemically unmodified sediments as well as restites may be entrained to greater depths and contribute to compositional heterogeneity in the deep mantle. Indeed, mineral inclusions with compositions indicative of subducted sedimentary protoliths (CAS-phase; K-hollandite; stishovite) have been reported in 'ultradeep' diamonds and suggest that deep subduction and survival of sediments occurs to at least transition zone depths [4]. With this in mind, we have performed laser heated diamond anvil cell experiments at pressures of 8-80 GPa on two anhydrous glass starting materials: a marine clay and the restite that is left after 50% melt extraction of this clay at 3 GPa and 800 °C [3]. We chose to work with an anhydrous version of the marine clay given that the investigated pressure range exceeds that of phengite stability [5], and phengite is the only hydrous phase in subducted sediments at UHP conditions. The clay was heated along a P-T path representative of a cold subduction geotherm, whereas the clay restite was heated along a hotter subduction geotherm consistent with low pressure melting. Phases were identified by synchrotron X-ray micro-diffraction at beamline I15 of the Diamond
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Deng, L.; Liu, X.; Liu, H.; Dong, J.
2010-12-01
The high pressure physical-chemical behaviors of feldspar in subducted slab are very important to the geodynamic process in the deep interior of the Earth. Albite (NaAlSi3O8;Ab) is one of the few end members in the feldspar family, and its high-P behavior is obviously a prerequisite to the full understanding of the physical-chemical properties of feldspar at high pressures. So far it has been well accepted that Ab breaks down to the phase assemblage of Jadeite+Stishovite(NaAlSi2O6; Jd, SiO2; St,JS hereafter) at ~9-10 GPa. The JS phase assemblage might be stable up to ~23 GPa, and eventually directly change into the phase assemblage of calcium-ferrite type NaAlSiO4 (Cf) +2St (CS hereafter). However, some independent researches suggest there is an intermediate phase Na-hollandite (Na-Hall; a phase with the composition of NaAlSi3O8 and the structure of hollandite) between JS phase assemblage transition into CS phase assemblage (Liu 1978; Tutti 2007; Sekine and Ahrens, 1992; Beck et al., 2004). Whether Na-Hall is a thermodynamic stable phase under high P-T conditions remains unknown. In this work, phase relations in the composition of albite NaAlSi3O8 at pressures up to 40 GPa were constrained by a theoretical method that combines the ab initio calculation and quasi-harmonic Debyemodel. First, the P-T dependence of the thermodynamic potentials of the individual phase, St, Cf, Jd and the hypothetical Na-Holl were derived. Our results are generally in consistent agreement with available experimental data and previous theoretical predictions. Second, the Gibbs free energy of the hypothetical Na-Holl phase was compared with that of the phase assemblages JS and CS. Our results show that the Na-Holl phase is not a thermodynamically stable phase over the studied P-T conditions of 0-40 GPa and 100-600 K, which rules it out as a possible intermediate phase along the transition path from the JS phase assemblage to CS phase assemblage. Our calculations have predicted that the JS
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Energy Technology Data Exchange (ETDEWEB)
Rapp, R.P.; Irifune, T.; Shimizu, N.; Nishiyama, N.; Norman, M.D.; Inoue, T. (Ehime U); (WHOI); (UC); (ANU)
2008-10-08
the product of melting of deeply recycled (subducted) Archean-age metasediments in the mantle transition zone [Murphy, D.T., Collerson, K.D., Kamber, B.S., 2002. Lamproites from Gaussberg, Antartica: possible transition zone melts of Archaean subducted sediments. J. Petrol. 43, 981-1001]. Here we report the results of phase equilibria experiments on two different natural sedimentary compositions (a high-grade metapelite with < 1 wt.% H{sub 2}O, and a marine 'mud' with 8 wt.% H{sub O}) at 16-23 GPa. In both materials, the high-pressure mineral assemblages contain {approx} 15-30 wt.% K-hollandite (KAlSi{sub 3}O{sub 8}), in addition to stishovite, garnet, an Al-silicate phase (kyanite or phase egg), and a Fe-Ti spinel (corundum). Ion microprobe analyses of K-hollandite for a range of trace elements reveal that this phase controls a significant proportion of the whole-rock budget of incompatible, large-ion lithophile elements (LILEs, e.g., Rb, Ba, Sr, K, Pb, La, Ce and Th). Comparisons between the abundances and ratios of these elements in K-hollandite with those in EM-I type ocean-island basalts from Pitcairn Island and related seamounts, and with the Gaussberg lamproites, indicate the presence of deeply recycled, continent-derived sediments in these lavas sources. Our results suggest that the incompatible trace-element signature of EM-I OIB reservoirs in general and of the Gaussberg lamproites in particular can be attributed to recycling of K-hollandite-bearing continental sediments to transition zone depths.
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Osmaston, Miles
2013-04-01
, including generating internally a very strong push-apart force, the straightness of MOR segments is the automatic result of accretion controlled by lateral cooling [8]. Olivine crystal has grossly anisotropic thermal conductivity, high on the a-axis [9] so, contrasting with the much lower conductivity of melt, suitably oriented ones on the crack walls grow the fastest and build in the seismic anisotropy from the start. For ophiolites, I will illustrate a close relative of this thick-plate model, but geared to their specific near-continent genesis and emplacement, which provides for their very real shearing and anisotropy at the crust-tectonite junction and for the 25 - 50 km metamorphic pressures in their soles [10]. A remarkably fertile model for the genesis of intraplate volcanism, without plumes, is also provided by this thick-plate perspective of plate dynamics [11]. We now move to deeper in the mantle. Attachment of the LVZ material to the ocean plate and the low conductivity of its interstial melt renders it still buoyant when the bigger ridge push makes it subduct [12]. Seismological transects of subduction zones show that this heat re-emerges at depth to partially melt the interface former oceanic crust, the result (on experimental evidence) being stishovitic residue plus (because of its compressibility) very dense ultramafic melt [12]. Both will shower into the lower mantle and eventually form layers on D'', the melt being prevented from freezing because that would need the energy to increase its volume. Hence the seismic anisotropy of D''. Moving still deeper, to the outer-core flows from which the Inner Core has grown. I attribute its cigar shape to preferential addition to its polar regions, from a downwelling flow, not to deformation of the IC, except perhaps as weak isostatic adjustment to that polar addition. I speculate that polar-aligned columnar growth of iron crystals, although themselves not strongly anisotropic, would impound 'less pure' alloy between
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13th International Conference on Films and Coatings
International Nuclear Information System (INIS)
2017-01-01
. For the first time this process was used to clean the surface of metals from radionuclides. The coefficient of purification at the level of 20 000 is the maximum compared to all existing methods. One of the new trends in the development of science and technology, reflected in the reports is the formation of pyrocarbon coatings in plasma of a vacuum arc discharge. For the first time such coating has been researched and applied to the electrodes of powerful generator tubes as antiemission coatings. Theoretically and experimentally were investigated the thermal processes during treatment of the inner surface of the cylindrical cavity by the cathode spots of a vacuum arc discharge. In a number of reports were reflected the characteristics of magnetron sputtering systems and principles of coatings deposition on their basis. The characteristics, technological aspects of production and results of testing of gradient coatings for aerospace optics were discussed. Promising technology of pulsed magnetron sputtering was noted. Possibilities of application of multilayer composite coatings in the systems of radiation protection of spacecraft were reviewed. Were shown the advantages of composite coatings before traditionally used in space technology aluminum alloys. At this Conference many reports were devoted to the formation of oxide coatings by different methods and for different fields of application. For example, the results of comparative studies of the original and processed in the plasma flow oxide microcomposites, consisting of TiO 2 , SiO 2 , Al 2 O 3 , and also plasma coatings from them – materials with amorphous-crystalline structure and a reinforced ultrafine phases of stishovite. It was shown that a reliable method of forming a specified surface nanorelief is a direct resistless lithography by a focused ion beam. The use of ions of different masses and energies significantly expands its abilities for nanoconstruction and nanoengineering of thin-layer structures