Hanns-Peter Liermann

The most incompressible metal osmium at static pressures above 750 gigapascals

Metallic osmium (Os) is one of the most exceptional elemental materials, having, at ambient pressure, the highest known density and one of the highest cohesive energies and melting temperatures. It is also very incompressible, but its high-pressure behaviour is not well understood because it has been studied so far only at pressures below 75 gigapascals. Here we report powder X-ray diffraction measurements on Os at multi-megabar pressures using both conventional and double-stage diamond anvil cells, with accurate pressure determination ensured by first obtaining self-consistent equations of state of gold, platinum, and tungsten in static experiments up to 500 gigapascals. These measurements allow us to show that Os retains its hexagonal close-packed structure upon compression to over 770 gigapascals. But although its molar volume monotonically decreases with pressure, the unit cell parameter ratio of Os exhibits anomalies at approximately 150 gigapascals and 440 gigapascals. Dynamical mean-field theory calculations suggest that the former anomaly is a signature of the topological change of the Fermi surface for valence electrons. However, the anomaly at 440 gigapascals might be related to an electronic transition associated with pressure-induced interactions between core electrons. The ability to affect the core electrons under static high-pressure experimental conditions, even for incompressible metals such as Os, opens up opportunities to search for new states of matter under extreme compression.

Structural complexity of simple Fe2O3 at high pressures and temperatures

Although chemically very simple, Fe2O3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe2O3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described by the homologous series nFeO·mFe2O3. Decomposition of Fe2O3 and Fe3O4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe5O7 and Fe25O32 phases with release of oxygen. Our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.

Structural complexity of simple Fe[subscript 2]O[subscript 3] at high pressures and temperatures

Although chemically very simple, Fe2O3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe2O3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described by the homologous series nFeO·mFe2O3. Decomposition of Fe2O3 and Fe3O4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe5O7 and Fe25O32 phases with release of oxygen. Our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.

Beamline P02.1 at PETRA III for high‐resolution and high‐energy powder diffraction

By providing the capabilities for high-resolution, high-energy and time-resolved powder X-ray diffraction, beamline P02.1 is a versatile tool to tackle various problems in materials science, crystallography and chemistry.

The Extreme Conditions Beamline P02.2 and the Extreme Conditions Science Infrastructure at PETRA III

Performance description of the Extreme Conditions Beamline (ECB, P02.2) at PETRA III that is optimized for micro-diffraction at simultaneous high pressure and high and low temperatures created in different diamond anvil cells environments. Additional information of the capabilities of the Extreme Conditions Science Infrastructure for DAC work is provided.

Strength and elasticity of niobium under high pressure

High purity polycrystalline niobium contained in boron-epoxy gasket was compressed in a diamond anvil cell (DAC). The pressure was increased in steps of ∼3 GPa and the diffraction patterns recorded at each pressure with the incident x-ray beam perpendicular to the load axis of the DAC (radial diffraction). The maximum pressure reached was 37.6 GPa. The compressive strength (differential stress) derived from the radial diffraction data is 0.44(1) GPa at 2.1 GPa and shows a shallow maximum at ∼5 GPa, and then decreases to 0.35(5) at 12 GPa. At higher pressures, strength increases nearly linearly and the extrapolated value at 40 GPa is 0.94(6) GPa. At any pressure, the single-crystal elastic moduli derived from the diffraction data can be made to match well those obtained from the extrapolation of the elasticity data at ambient pressure by adjusting the weight parameter α that appears in the lattice strain theory. The parameter α is found to decrease from 2.00(8) at 2.1 GPa to 1.35(4) at 37.6 GPa.

Distinct thermal behavior of GeO2 glass in tetrahedral, intermediate, and octahedral forms

One fascinating high-pressure behavior of tetrahedral glasses and melts is the local coordination change with increasing pressure, which provides a structural basis for understanding numerous anomalies in their high-pressure properties. Because the coordination change is often not retained upon decompression, studies must be conducted in situ. Previous in situ studies have revealed that the short-range order of tetrahedrally structured glasses and melts changes above a threshold pressure and gradually transforms to an octahedral form with further pressure increase. Here, we report a thermal effect associated with the coordination change at given pressures and show distinct thermal behaviors of GeO2 glass in tetrahedral, octahedral, and their intermediate forms. An unusual thermally induced densification, as large as 16%, was observed on a GeO2 glass at a pressure of 5.5 gigapascal (GPa), based on in situ density and x-ray diffraction measurements at simultaneously high pressures and high temperatures. The large thermal densification at high pressure was found to be associated with the 4- to 6-fold coordination increase. Experiments at other pressures show that the tetrahedral GeO2 glass displayed small thermal densification at 3.3 GPa arising from the relaxation of intermediate range structure, whereas the octahedral glass at 12.3 GPa did not display any detectable thermal effects.

Novel high pressure monoclinic Fe2O3 polymorph revealed by single-crystal synchrotron X-ray diffraction studies

A novel high pressure polymorph of iron sesquioxide, m-Fe2O3, has been identified by means of single-crystal synchrotron X-ray diffraction (XRD). Upon compression of a single crystal of hematite, α-Fe2O3, in a diamond anvil cell, the transition occurs at pressure of about 54 GPa and results in ∼10% volume reduction. The crystal structure of the new phase was solved by the direct method (monoclinic space group P21/n, a=4.588(3), b=4.945(2), c=6.679(7) Å and β=91.31(9)°) and refined to R1 ∼11%. It belongs to the cryolite double-perovskite structure type and consists of corner-linked FeO6 octahedra and FeO6 trigonal prisms filling the free space between the octahedra. Upon compression up to ∼71 GPa at ambient temperature no further phase transitions were observed. Laser heating to ∼ 2100±100 K promotes a transition to the Cmcm CaIrO3-type (post-perovskite (PPv)) phase. The PPv-Fe2O3 crystal structure was refined by means of single-crystal XRD at ∼65 GPa. On decompression the PPv-Fe2O3 phase fully transforms back to hematite at pressures between ∼25 and 15 GPa.

Stability of Fe,Al-bearing bridgmanite in the lower mantle and synthesis of pure Fe-bridgmanite

A study of Fe,Al-bearing bridgmanite in Earth‘s mantle and synthesis of pure Fe-bridgmanite with anomalously low compressibility. The physical and chemical properties of Earth’s mantle, as well as its dynamics and evolution, heavily depend on the phase composition of the region. On the basis of experiments in laser-heated diamond anvil cells, we demonstrate that Fe,Al-bearing bridgmanite (magnesium silicate perovskite) is stable to pressures over 120 GPa and temperatures above 3000 K. Ferric iron stabilizes Fe-rich bridgmanite such that we were able to synthesize pure iron bridgmanite at pressures between ~45 and 110 GPa. The compressibility of ferric iron–bearing bridgmanite is significantly different from any known bridgmanite, which has direct implications for the interpretation of seismic tomography data.

High-pressure behavior of synthetic mordenite-Na: an in situ single-crystal synchrotron X-ray diffraction study

Abstract The high-pressure behavior of a synthetic mordenite-Na (space group: Cmcm or Cmc21) was studied by in situ single-crystal synchrotron X-ray diffraction with a diamond anvil cell up to 9.22(7) GPa. A phase transition, likely displacive in character, occurred between 1.68(7) and 2.70(8) GPa, from a C-centered to a primitive space group: possibly Pbnm, Pbnn or Pbn21. Fitting of the experimental data with III-BM equations of state allowed to describe the elastic behavior of the high-pressure polymorph with a primitive lattice. A very high volume compressibility [KV0 = 25(2) GPa, βV0 = 1/KV0 = 0.040(3) GPa–1; KV′ = (?KV/?P)T = 2.0(3)], coupled with a remarkable elastic anisotropy (βb>>βc>βa), was found. Interestingly, the low-P and high-P polymorphs show the same anisotropic compressional scheme. A structure collapse was not observed up to 9.22(7) GPa, even though a strong decrease of the number of observed reflections at the highest pressures suggests an impending amorphization. The structure refinements performed at room-P, 0.98(2) and 1.68(7) GPa allowed to describe, at a first approximation, the mechanisms that govern the framework deformation in the low-P regime: the bulk compression is strongly accommodated by the increase of the ellipticity of the large 12-membered ring channels running along [001].