Synthesis and Microdiffraction at Extreme Pressures and Temperatures

High pressure compounds and polymorphs are investigated for a broad range of purposes such as determine structures and processes of deep planetary ...

University of Chicago

Alumina (alpha-Al(2)O(3)) has been widely used as a pressure calibrant in static high-pressure experiments and as a window material in dynamic shock-wave experiments; it is also a model material in ceramic science. So understanding its high-pressure stability and physical properties is crucial for interpreting such experimental data, and for testing theoretical calculations. Here we report an in situ X-ray diffraction study of alumina (doped with Cr(3+)) up to 136 GPa and 2,350 K. We observe a phase transformation that occurs above 96 GPa and at high temperatures. Rietveld full-profile refinements show that the high-pressure phase has the Rh(2)O(3) (II) (Pbcn) structure, consistent with theoretical predictions. This phase is structurally related to corundum, but the AlO(6) polyhedra are highly distorted, with the interatomic bond lengths ranging from 1.690 to 1.847 A at 113 GPa. Ruby luminescence spectra from Cr(3+) impurities within the quenched samples under ambient conditions show significant red shifts and broadening, consistent with the different local environments of chromium atoms in the high-pressure structure inferred from diffraction. Our results suggest that the ruby pressure scale needs to be re-examined in the high-pressure phase, and that shock-wave experiments using sapphire windows need to be re-evaluated.

Crystal structure of a high-pressure/high-temperature phase of alumina by in situ X-ray diffraction.

Recent developments in high-pressure methods and advances in X-ray crystallography have led to a new level of understanding of phase diagrams and structures of materials under pressure. Recently discovered phenomena such as complex phases of alkali metals, incommensurate host-guest structures, and incommensurately modulated structures have rendered obsolete our conventional wisdom about the range of structures possible in the elements. Using new in situ diffraction techniques, we have resolved the long-standing problem of the phase-transition sequence of sulphur in its non-metallic state. We demonstrate that it is very different from that previously proposed, with only two phases stable between 1.5 GPa and 83 GPa (the pressure of metallization), and temperatures from 300 K to 1,100 K. The phases have a triangular chain and a squared chain structure. The same squared chain structure is found in the heavier group VI element selenium.

Novel chain structures in group VI elements.

This study demonstrates the use of monochromatic synchrotron X-ray radiation of 40 keV for high-precision equation-of-state studies on sets of single crystals analysed individually in the same diamond-anvil pressure cell. Angle-dispersive zone-axis diffraction patterns were obtained from crystals of wustite-Fe0.93O and magnesiowÃ¼stite-(Mg0.73Fe0.27)O to 51 GPa in a hydrostatic helium pressure medium. The rhombohedral phase of Fe0.93O was observed above 23 GPa, and its isothermal bulk modulus (K0) was determined to be 134 (+/-4) GPa, assuming K'=4. The rhombohedral phase of Fe(0.93)O is more compressible than B1-structured Fe0.93O, with K0=146 (+/-2) GPa. MagnesiowÃ¼stite-(Mg0.73Fe0.27)O remains cubic over the experimental pressure range, and has a bulk modulus of 154 (+/-3) GPa with K'=4.0 (+/-0.1).

Single-crystal synchrotron X-ray diffraction study of wÃ¼stite and magnesiowÃ¼stite at lower-mantle pressures.

Polychromatic single-crystal diffraction (pSXD) offers important advantages compared with monochromatic diffraction, such as ultrafast data collection and the ability to collect diffraction data without sample rotation. Despite the relevance of these advantages for applications in high-pressure experiments, pSXD has never been successfully applied for full structure determination at high pressure. Here the theory of polychromatic microdiffraction, strategies developed to adapt it to high-pressure applications, and results of pilot experiments are described. Special emphasis is placed on experiments with microcrystals and multigrain aggregates, and on the use of monochromator scans to extend the pressure range for single-crystal structure determination to the megabar region. Closely related applications to materials research problems are also discussed.

Adapting polychromatic X-ray microdiffraction techniques to high-pressure research: energy scan approach.

A piezoelectric material is one that generates a voltage in response to a mechanical strain (and vice versa). The most useful piezoelectric materials display a transition region in their composition phase diagrams, known as a morphotropic phase boundary, where the crystal structure changes abruptly and the electromechanical properties are maximal. As a result, modern piezoelectric materials for technological applications are usually complex, engineered, solid solutions, which complicates their manufacture as well as introducing complexity in the study of the microscopic origins of their properties. Here we show that even a pure compound, in this case lead titanate, can display a morphotropic phase boundary under pressure. The results are consistent with first-principles theoretical predictions, but show a richer phase diagram than anticipated; moreover, the predicted electromechanical coupling at the transition is larger than any known. Our results show that the high electromechanical coupling in solid solutions with lead titanate is due to tuning of the high-pressure morphotropic phase boundary in pure lead titanate to ambient pressure. We also find that complex microstructures or compositions are not necessary to obtain strong piezoelectricity. This opens the door to the possible discovery of high-performance, pure-compound electromechanical materials, which could greatly decrease costs and expand the utility of piezoelectric materials.

Origin of morphotropic phase boundaries in ferroelectrics.

Closed electron shell systems, such as hydrogen, nitrogen or group 18 elements, can form weakly bound stoichiometric compounds at high pressures. An understanding of the stability of these van der Waals compounds is lacking, as is information on the nature of their interatomic interactions. We describe the formation of a stable compound in the Xe-H(2) binary system, revealed by a suite of X-ray diffraction and optical spectroscopy measurements. At 4.8 GPa, a unique hydrogen-rich structure forms that can be viewed as a tripled solid hydrogen lattice modulated by layers of xenon, consisting of xenon dimers. Varying the applied pressure tunes the Xe-Xe distances in the solid over a broad range from that of an expanded xenon lattice to the distances observed in metallic xenon at megabar pressures. Infrared and Raman spectra indicate a weakening of the intramolecular covalent bond as well as persistence of semiconducting behaviour in the compound to at least 255 GPa.

Pressure-induced bonding and compound formation in xenon-hydrogen solids.

Phases of the iron-oxygen binary system are significant to most scientific disciplines, directly affecting planetary evolution, life, and technology. Iron oxides have unique electronic properties and strongly interact with the environment, particularly through redox reactions. The iron-oxygen phase diagram therefore has been among the most thoroughly investigated, yet it still holds striking findings. Here, we report the discovery of an iron oxide with formula Fe(4)O(5), synthesized at high pressure and temperature. The previously undescribed phase, stable from 5 to at least 30 GPa, is recoverable to ambient conditions. First-principles calculations confirm that the iron oxide here described is energetically more stable than FeO + Fe(3)O(4) at pressure greater than 10 GPa. The calculated lattice constants, equation of states, and atomic coordinates are in excellent agreement with experimental data, confirming the synthesis of Fe(4)O(5). Given the conditions of stability and its composition, Fe(4)O(5) is a plausible accessory mineral of the Earth's upper mantle. The phase has strong ferrimagnetic character comparable to magnetite. The ability to synthesize the material at accessible conditions and recover it at ambient conditions, along with its physical properties, suggests a potential interest in Fe(4)O(5) for technological applications.

Discovery of the recoverable high-pressure iron oxide Fe4O5.

Diamond anvil cell (DAC), synchrotron X-ray diffraction (XRD), and small-angle X-ray scattering (SAXS) techniques are used to probe the composition inside hollow Î³-Fe(3)O(4) nanoparticles (NPs). SAXS experiments on 5.2, 13.3, and 13.8 nm hollow-shell Î³-Fe(3)O(4) NPs, and 6 nm core/14.8 nm hollow-shell Au/Fe(3)O(4) NPs, reveal the significantly high (higher than solvent) electron density of the void inside the hollow shell. In high-pressure DAC experiments using Ne as pressure-transmitting medium, formation of nanocrystalline Ne inside hollow NPs is not detected by XRD, indicating that the oxide shell is impenetrable. Also, FTIR analysis on solutions of hollow-shell Î³-Fe(3)O(4) NPs fragmented upon refluxing shows no evidence of organic molecules from the void inside, excluding the possibility that organic molecules get through the iron oxide shell during synthesis. High-pressure DAC experiments on Au/Fe(3)O(4) core/hollow-shell NPs show good transmittance of the external pressure to the gold core, indicating the presence of the pressure-transmitting medium in the gap between the core and the hollow shell. Overall, our data reveal the presence of most likely small fragments of iron and/or iron oxide in the void of the hollow NPs. The iron oxide shell seems to be non-porous and impenetrable by gases and liquids.

How "hollow" are hollow nanoparticles?

Knowledge of the structural properties of mantle phases is critical for understanding the enigmatic seismic features observed in the Earth's lower mantle down to the core-mantle boundary. However, our knowledge of lower mantle phase equilibria at high pressure (P) and temperature (T) conditions has been based on limited information provided by powder X-ray diffraction technique and theoretical calculations. Here, we report the in situ single-crystal structure determination of (Mg,Fe)SiO3 postperovskite (ppv) at high P and after temperature quenching in a diamond anvil cell. Using a newly developed multigrain single-crystal X-ray diffraction analysis technique in a diamond anvil cell, crystallographic orientations of over 100 crystallites were simultaneously determined at high P in a coarse-grained polycrystalline sample containing submicron ppv grains. Conventional single-crystal structural analysis and refinement methods were applied for a few selected ppv crystallites, which demonstrate the feasibility of the in situ study of crystal structures of submicron crystallites in a multiphase polycrystalline sample contained within a high P device. The similarity of structural models for single-crystal Fe-bearing ppv (~10 mol% Fe) and Fe-free ppv from previous theoretical calculations suggests that the Fe content in the mantle has a negligible effect on the crystal structure of the ppv phase.

Przemyslaw Dera

GeoSoilEnviroCARS

University of Chicago

Synthesis and Microdiffraction at Extreme Pressures and Temperatures

Przemyslaw Dera

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University of Chicago

Synthesis and Microdiffraction at Extreme Pressures and Temperatures

GeoSoilEnviroCARS