skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: High-pressure experimental study of tetragonal CaSiO3-perovskite to 200 GPa
Abstract In this study, we have investigated the crystal structure and equation of state of tetragonal CaSiO3-perovskite up to 200 GPa using synchrotron X-ray diffraction in laser-heated diamond-anvil cells. X-ray diffraction patterns of the quenched CaSiO3-perovskite above 148 GPa clearly show that 200, 211, and 220 peaks of the cubic phase split into 004+220, 204+312, and 224+400 peak pairs, respectively, in the tetragonal structure, and their calculated full-width at half maximum (FWHM) exhibits a substantial increase with pressure. The distribution of diffraction peaks suggests that the tetragonal CaSiO3-perovskite most likely has an I4/mcm space group at 300 K between 148 and 199 GPa, although other possibilities might still exist. Using the Birch-Murnaghan equations, we have determined the equation of state of tetragonal CaSiO3-perovskite, yielding the bulk modulus K0T = 227(21) GPa with the pressure derivative of the bulk modulus, K0T′ = 4.0(3). Modeled sound velocities at 580 K and around 50 GPa using our results and literature values show the difference in the compressional (VP) and shear-wave velocity (VS) between the tetragonal and cubic phases to be 5.3 and 6.7%, respectively. At ~110 GPa and 1000 K, this phase transition leads to a 4.3 and 9.1% jump in VP and VS, respectively. Since the addition of Ti can elevate the transition temperature, the transition from the tetragonal to cubic phase may have a seismic signature compatible with the observed mid-lower mantle discontinuity around the cold subduction slabs, which needs to be explored in future studies.  more » « less
Award ID(s):
1916941
PAR ID:
10317878
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
American Mineralogist
Volume:
107
Issue:
1
ISSN:
0003-004X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; (, American Mineralogist)
    Abstract While the water storage capacities of the upper 700 km depths of the mantle have been constrained by high-pressure experiments and diamond inclusion studies, the storage capacity of the lower mantle remains controversial. A recent high-pressure experimental study on CaSiO3 perovskite, which is the third most abundant mineral in the lower mantle, reported possible storage of H2O up to a few weight percent. However, the substitution mechanism for H in this phase remains unknown. We have conducted a series of density functional theory calculations under static-lattice conditions and high pressures to elucidate hydration mechanisms at the atomic scale. All of the possible dodecahedral (Ca2+ → 2H+) and octahedral (Si4+ → 4H+) substitution configurations for a tetragonal perovskite lattice have very small energy differences, suggesting the coexistence of multiples of H configurations in CaSiO3 perovskite at mantle pressures and temperatures. The dodecahedral substitutions decrease the bulk modulus, resulting in a smaller unit-cell volume of hydrous CaSiO3 perovskite under pressure, consistent with the experimental observations. Although the octahedral substitutions also decrease the bulk modulus, they increase the unit-cell volume at 1 bar. The H atoms substituted in the dodecahedral sites develop much less hydrogen bonding with O atoms, leading to a large distortion in the neighboring SiO6 octahedra. Such distortion may be responsible for the non-cubic peak splittings observed in experiments on hydrous CaSiO3 perovskite. Our calculated infrared spectra suggest that the observed broad OH modes in CaSiO3 perovskite can result from the existence of multiples of H configurations in the phase. Combined with the recent experimental results, our study suggests that CaSiO3 can be an important mineral phase to consider for the H2O storage in the lower mantle. 
    more » « less
  2. ; ; ; ; (, American Mineralogist)
    Abstract The influence of Al substitution on the elastic properties of stishovite and its transition to post-stishovite is of great importance for interpreting the seismic wave velocities of subducted mid-ocean ridge basalt (MORB) within the mantle transition zone and the lower mantle. However, atomistic mechanisms of Al substitution effects on the transition and its associated elasticity remain debated. Here synchrotron single-crystal X-ray diffraction measurements have been performed at room temperature on Al1.3-SiO2 (1.3 mol% Al in the chemical formula of Si0.965(3)Al0.041(1)O2H0.017(4)) and Al2.1-SiO2 (2.1 mol% Al in Si0.948(2)Al0.064(1)O2H 0.018(3)) crystals in diamond anvil cells with Boehler-Almax designed anvils up to 38.0 GPa and 28.5 GPa, respectively. Refinements of the diffraction patterns show that a transformation from stishovite (space group P42/mnm; No. 136) to CaCl2-typed post-stishovite (space group Pnnm; No. 58) is accompanied by splitting of O coordinates. The Al substitution in stishovite results in a faster decrease in the O coordinate, softer apical (Si,Al)-O bonds, and a softer and less distorted (Si,Al)O6 octahedron under compression. This leads to reduced adiabatic bulk modulus (KS), shear modulus (G), shear wave velocity (VS), and compressional wave velocity (VP) in the stishovite phase, explaining seismic wave perturbations in the mantle transition zone. Together with Raman data, Landau theory modeling shows that Al substitution increases the order parameter and excess free energy, stabilizing the post-stishovite phase at lower pressures. Correlation between elasticity and octahedral distortion index (D) reveals that at certain D, the Al substitution reduces KS, G, VS, and VP of the stishovite phase while increasing G, VS, and VP of the post-stishovite phase. Importantly, the maximum shear reduction is slightly enhanced at D = 0.00620(9) at the transition point. Our results help explain the seismically observed small-scale VS anomalies beneath subduction regions in the shallow lower mantle where Al,H-bearing stishovite undergoes the post-stishovite transition. 
    more » « less
  3. ; ; ; ; ; ; ; (, American Mineralogist)
    Abstract Davemaoite (CaSiO3 perovskite) is considered the third most abundant phase in the pyrolytic lower mantle and the second most abundant phase in the subducted mid-ocean ridge basalt (MORB). During the partial melting of the pyrolytic upper mantle, incompatible titanium (Ti) becomes enriched in the basaltic magma, forming Ti-rich MORB. Davemaoite is considered an important Ti-bearing mineral in subducted slabs by forming a Ca(Si,Ti)O3 solid solution. However, the crystal structure and compressibility of Ca(Si,Ti)O3 perovskite solid solution at relevant pressure and temperature conditions had not been systematically investigated. In this study, we investigated the structure and equations of state of Ca(Si0.83Ti0.17)O3 and Ca(Si0.75Ti0.25)O3 perovskites at room temperature up to 82 and 64 GPa, respectively, by synchrotron X-ray diffraction (XRD). We found that both Ca(Si0.83Ti0.17)O3 and Ca(Si0.75Ti0.25)O3 perovskites have a tetragonal structure up to the maximum pressures investigated. Based on the observed data and compared to pure CaSiO3 davemaoite, both Ca(Si0.83Ti0.17)O3 and Ca(Si0.75Ti0.25)O3 perovskites are expected to be less dense up to the core-mantle boundary (CMB), and specifically ~1–2% less dense than CaSiO3 davemaoite in the pressure range of the transition zone (15–25 GPa). Our results suggest that the presence of Ti-bearing davemaoite phases may result in a reduction in the average density of the subducting slabs, which in turn promotes their stagnation in the lower mantle. The presence of low-density Ti-bearing davemaoite phases and subduction of MORB in the lower mantle may also explain the seismic heterogeneity in the lower mantle, such as large low shear velocity provinces (LLSVPs). 
    more » « less
  4. ; ; ; ; ; ; ; ; ; ; et al (, American Mineralogist)
    Abstract Synthetic thorite and huttonite, two polymorphs of ThSiO4, were investigated by a combination of in situ high-pressure synchrotron X-ray powder diffraction and in situ high pressure Raman spectroscopy. The average onset pressure of the thorite-to-huttonite transition was determined to be 6.6 ± 0.2 GPa, using both techniques. The bulk moduli of thorite and huttonite were determined to be 139(9) and 246(11) GPa, respectively, by fitting their unit-cell volume data to a second order Birch-Murnaghan equation of state (EOS). Based on its bulk modulus, thorite is the most compressible zircon-structured orthosilicate, as it has the largest unit cell volume among tetravalent metal orthosilicates. The pressure derivatives of the vibrational modes of thorite were found to be consistent with those previously reported for other orthosilicates (e.g., zircon, hafnon, stetindite, and coffinite), while having the smallest Grüneisen parameter. A new P-T phase diagram for ThSiO4 is proposed, where the boundary of the thorite → huttonite transition is: P(T) = (7.8 ± 0.9 GPa) − (0.006 ± 0.002 GPa/K)T. Based on the new P-T phase diagram, we further estimated the enthalpy of formation of huttonite, ΔHf,ox, to be 0.6 ± 6.0 kJ/mol, suggesting its metastability and rare locality in nature. 
    more » « less
  5. ; ; ; ; ; ; ; ; ; (, Journal of Applied Physics)
    High-entropy alloys (HEAs) are a class of multi-element materials that exhibit unique structural and functional properties. This study reports on the synthesis and characterization of a superconducting HEA, (NbTa)0.55(HfTiZr)0.45 fabricated using the vacuum arc melting technique. Scanning electron microscopy and energy-dispersive x-ray spectroscopy were employed to analyze the material's morphology and composition. X-ray diffraction analysis revealed a single-phase body-centered cubic (BCC) structure with a measured nanoindentation hardness of 6.4 GPa and Young's modulus of 132 GPa. This HEA superconductor was investigated by x-ray diffraction at Beamline 13BM-C, Advanced Photon Source, and the BCC phase was stable to the highest pressure of 50 GPa. Superconductivity was characterized by four-probe resistivity measurements in a quantum design physical property measurement system, yielding a superconducting transition temperature (Tc) of 7.2 K at ambient pressure and reaching a maximum of 10.1 K at the highest applied pressure of 23.6 GPa. The combination of high structural stability enhanced superconducting performance under pressure and superior mechanical properties highlights (NbTa)0.55(HfTiZr)0.45 as a promising superconductor under extreme environments. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email