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Greenberg, Eran

Publications and source records attributed to Greenberg, Eran.

35 records · Page 2

Novel Hydrogen Clathrate Hydrate

We report a new hydrogen clathrate hydrate synthesized at 1.2 GPa and 298 K documented by single-crystal x-ray diffraction, Raman spectroscopy, and first-principles calculations. The oxygen sublattice of the new clathrate hydrate matches that of ice II, while hydrogen molecules are in the ring cavities, which results in the trigonal R3c or R¯3c space group (proton ordered or disordered, respectively) and the composition of ( H 2 O) 6 H 2 . Raman spectroscopy and theoretical calculations reveal a hydrogen disordered nature of the new phase $C$$^{'}_{1}$, distinct from the well-known ordered C 1 clathrate, to which this new structure transforms upon compression and/or cooling. Furthermore, this new clathrate phase can be viewed as a realization of a disordered ice II, unobserved before, in contrast to all other ordered ice structures.

36 MATERIALS SCIENCE↗

High pressure chemical reactivity and structural study of the Na–P and Li–P systems

In this work, the Na–P and Li–P chemical systems were studied under pressure using synchrotron X-ray diffraction in a diamond anvil cell up to 20 GPa, combined with the AIRSS ab initio random structure searching technique. The results reveal an enhanced reactivity of both alkali metals with phosphorous at slightly elevated pressures. This enables the synthesis of Li 3 P and Na 3 P at room temperature (RT) starting from element precursors, bypassing the established chemical synthesis methods. Both compounds undergo a pressure-induced phase transition from the hexagonal Na 3 As-type structure (stable at ambient conditions) towards a Fm m (FCC) structure that remains stable up to 20 GPa. Attempts to synthesize compounds with higher alkali metal content (such as Li 5 P) using high-temperature and -pressure conditions (up to 2000+ K and 30 GPa), inspired by recent theoretical predictions, were not successful.

25 ENERGY STORAGE↗

A new hydrous iron oxide phase stable at mid-mantle pressures

The amount of hydrogen stored in the Earth's interior is important for a range of issues, including the volatile incorporation during the Earth formation and the co-evolution of the atmosphere, the hydrosphere, and the interior. Recent experiments found titanium bearing ε-FeOOH in a hydrous basaltic system at 12–19 GPa and 1300 K. Pyrite-type FeOOH was found to be stable at pressures higher than 80 GPa. These discoveries suggest possible hydrogen storage in the mantle transition zone and in the mantle below 1800 km depths, respectively. However, it remains uncertain how the potential deep hydrogen storage can be connected to the shallower storage. Here, we report a new hydrous iron oxide (η-Fe 12 O 18+x / 2 H x , x ≈ 2) stable at pressures between the stability fields of the ε- and the pyrite-type FeOOH. Our experiment also shows that the new η phase can exist together with the major lower mantle minerals including bridgmanite and periclase, making it an important hydrogen-bearing phase in the Earth's deep interior. Because of its limited H 2 O storage capacity, which is less than 1/6 of the storage capacity of the pyrite-type phase and the ε phase, the stability of the η phase would result in H 2 O loss during water transport in the mid mantle and therefore limit the amount of H 2 O potentially stored in the Fe–O–H system of the lower mantle. As a result, the large channel in the crystal structure of the η phase could provide potential storage sites for other volatile elements in the deep mantle.

58 GEOSCIENCES↗

A Boosted Critical Temperature of 166 K in Superconducting D 3 S Synthesized from Elemental Sulfur and Hydrogen

The discovery of superconductivity in H 3 S at 203 K marked an advance towards room-temperature superconductivity and demonstrated the potential of H-dominated compounds to possess a high critical temperature (T c ). There have been numerous reports of the H-S system over the last five years, but important questions remain unanswered. It is crucial to verify whether the Tc was determined correctly for samples prepared from compressed H 2 S, since they are inevitably contaminated with H-depleted byproducts. Here, we prepare stoichiometric H 3 S by direct in situ synthesis from elemental S and excess H 2 . The Im$_\bar{3}$ m phase of D 3 S samples exhibits a T c significantly higher than previously reported values (ca. 150 K), reaching a maximum T c of 166 K at 157 GPa. Furthermore, we confirm that the sharp decrease in T c below 150 GPa is accompanied by continuous rhombohedral structural distortions and demonstrate that the Cccm phase is nonmetallic, with molecular H 2 units in the crystal structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pressure-induced crystallization of an amorphous martensite alloy

Recently, solid-state amorphization through temperature-induced martensitic transition has been reported. The stability of the amorphous martensite phase, which co-exists with a crystalline counterpart, is intriguing but remains ill-defined. In this work, we studied the structural stability of a Ti 59.1 Zr 37 Cu 2.3 Fe 1.6 amorphous martensite alloy by combining in situ high-pressure synchrotron x-ray diffraction with ex situ transmission electron microscopy. During compression at room temperature, an irreversible pressure-induced crystallization of the amorphous martensite phase into a β-Ti phase is revealed. Qualitative analysis reveals the important role of the local atomic strain in stabilizing/destabilizing amorphous martensite alloys and its high tunability of the local atomic strain under high pressure.

36 MATERIALS SCIENCE↗

Effects of composition and pressure on electronic states of iron in bridgmanite

Electronic states of iron in the lower mantle's dominant mineral, (Mg,Fe,Al)(Fe,Al,Si)O 3 bridgmanite, control physical properties of the mantle including density, elasticity, and electrical and thermal conductivity. However, the determination of electronic states of iron has been controversial, in part due to different interpretations of Mössbauer spectroscopy results used to identify spin state, valence state, and site occupancy of iron. We applied energy-domain Mössbauer spectroscopy to a set of four bridgmanite samples spanning a wide range of compositions: 10–50% Fe/total cations, 0–25% Al/total cations, 12–100% Fe 3+ /total Fe. Measurements performed in the diamond-anvil cell at pressures up to 76 GPa below and above the high to low spin transition in Fe 3+ provide a Mössbauer reference library for bridgmanite and demonstrate the effects of pressure and composition on electronic states of iron. Results indicate that although the spin transition in Fe 3+ in the bridgmanite B-site occurs as predicted, it does not strongly affect the observed quadrupole splitting of 1.4 mm/s, and only decreases center shift for this site to 0 mm/s at ~70 GPa. Thus center shift can easily distinguish Fe 3+ from Fe 2+ at high pressure, which exhibits two distinct Mössbauer sites with center shift ~1 mm/s and quadrupole splitting 2.4–3.1 and 3.9 mm/s at ~70 GPa. Correct quantification of Fe 3+ /total Fe in bridgmanite is required to constrain the effects of composition and redox states in experimental measurements of seismic properties of bridgmanite. Furthermore, in Fe-rich, mixed-valence bridgmanite at deep-mantle-relevant pressures, up to ~20% of the Fe may be a Fe 2.5+ charge transfer component, which should enhance electrical and thermal conductivity in Fe-rich heterogeneities at the base of Earth's mantle.

58 GEOSCIENCES↗

Hydrous olivine alteration on Mars and Earth

In this report hydrous alteration of olivine macrocrysts in a Martian olivine phyric basalt, NWA 10416, and a terrestrial basalt from southern Colorado are examined using SEM, EPMA, TEM, and µXRD techniques. The olivines in the meteorite contain linear nanotubes of hydrous material, amorphous areas, and fluid dissolution textures quite distinct from alteration identified in other Martian meteorites. Instead, they bear resemblance to terrestrial deuteric alteration features. The presence of the hydrous alteration phase Mg‐laihunite within the olivines has been confirmed by µXRD analysis. The cores of the olivines in both Martian and terrestrial samples are overgrown by unaltered rims whose compositions match those of a separate population of groundmass olivines, suggesting that the core olivines are xenocrysts whose alteration preceded crystallization of the groundmass. The terrestrial sample is linked to deep crustal metasomatism and the “ignimbrite flare‐up” of the Oligocene epoch. The comparison of the two samples suggests the existence of an analogous relatively water‐rich magmatic reservoir on Mars.

58 GEOSCIENCES↗