Atomic and Electronic Structure in MgO-SiO2.

Understanding disordered structure is difficult due to insufficient information in experimental data. Here, we overcome this issue by using a combination of diffraction and simulation to investigate oxygen packing and network topology in glassy (g-) and liquid (l-) MgO-SiO2 based on a comparison with the crystalline topology. We find that packing of oxygen atoms in Mg2SiO4 is larger than that in MgSiO3, and that of the glasses is larger than that of the liquids. Moreover, topological analysis suggests that topological similarity between crystalline (c)- and g-(l-) Mg2SiO4 is the signature of low glass-forming ability (GFA), and high GFA g-(l-) MgSiO3 shows a unique glass topology, which is different from c-MgSiO3. We also find that the lowest unoccupied molecular orbital (LUMO) is a free electron-like state at a void site of magnesium atom arising from decreased oxygen coordination, which is far away from crystalline oxides in which LUMO is occupied by oxygen's 3s orbital state in g- and l-MgO-SiO2, suggesting that electronic structure does not play an important role to determine GFA. We finally concluded the GFA of MgO-SiO2 binary is dominated by the atomic structure in terms of network topology.

Revisiting the melting curve of H2O by Brillouin spectroscopy to 54 GPa.

The melting curve of H2O was investigated up to 54 GPa and ∼2000 K by Brillouin scattering spectroscopy in a diamond anvil cell. A CO2 laser was used for heating the H2O sample directly in order to reduce the risk of chemical reactions. The melting was identified based on the appearance of the Brillouin peaks derived from the liquid phase. The longitudinal wave velocity (Vp) of the liquid phase along the melting curve exhibits a smooth increase with pressure. The melting temperature of H2O shows no kink previously reported but a monotonic increase between 26 and 54 GPa. Present melting data suggest that the melting occurs from body-centered-cubic superionic phase in the pressure-temperature range investigated.

Structure of alumina glass.

The fabrication of novel oxide glass is a challenging topic in glass science. Alumina (Al2O3) glass cannot be fabricated by a conventional melt-quenching method, since Al2O3 is not a glass former. We found that amorphous Al2O3 synthesized by the electrochemical anodization of aluminum metal shows a glass transition. The neutron diffraction pattern of the glass exhibits an extremely sharp diffraction peak owing to the significantly dense packing of oxygen atoms. Structural modeling based on X-ray/neutron diffraction and NMR data suggests that the average Al-O coordination number is 4.66 and confirms the formation of OAl3 triclusters associated with the large contribution of edge-sharing Al-O polyhedra. The formation of edge-sharing AlO5 and AlO6 polyhedra is completely outside of the corner-sharing tetrahedra motif in Zachariasen's conventional glass formation concept. We show that the electrochemical anodization method leads to a new path for fabricating novel single-component oxide glasses.

Relationship between diffraction peak, network topology, and amorphous-forming ability in silicon and silica.

The network topology in disordered materials is an important structural descriptor for understanding the nature of disorder that is usually hidden in pairwise correlations. Here, we compare the covalent network topology of liquid and solidified silicon (Si) with that of silica (SiO2) on the basis of the analyses of the ring size and cavity distributions and tetrahedral order. We discover that the ring size distributions in amorphous (a)-Si are narrower and the cavity volume ratio is smaller than those in a-SiO2, which is a signature of poor amorphous-forming ability in a-Si. Moreover, a significant difference is found between the liquid topology of Si and that of SiO2. These topological features, which are reflected in diffraction patterns, explain why silica is an amorphous former, whereas it is impossible to prepare bulk a-Si. We conclude that the tetrahedral corner-sharing network of AX2, in which A is a fourfold cation and X is a twofold anion, as indicated by the first sharp diffraction peak, is an important motif for the amorphous-forming ability that can rule out a-Si as an amorphous former. This concept is consistent with the fact that an elemental material cannot form a bulk amorphous phase using melt quenching technique.

Structure of disordered materials under ambient to extreme conditions revealed by synchrotron x-ray diffraction techniques at SPring-8-recent instrumentation and synergic collaboration with modelling and topological analyses.

The structure of disordered materials is still not well understood because of insufficient experimental data. Indeed, diffraction patterns from disordered materials are very broad and can be described only in pairwise correlations because of the absence of translational symmetry. Brilliant hard x-rays from third-generation synchrotron radiation sources enable us to obtain high-quality diffraction data for disordered materials from ambient to high temperature and high pressure, which has significantly improved our grasp of the nature of order in disordered materials. Here, we introduce the progress in the instrumentation for hard x-ray beamlines at SPring-8 over the last 20 years with associated results and advanced data analysis techniques to understand the topology in disordered materials.

Fluid-like elastic response of superionic NH3 in Uranus and Neptune.

Nondipolar magnetic fields exhibited at Uranus and Neptune may be derived from a unique geometry of their icy mantle with a thin convective layer on top of a stratified nonconvective layer. The presence of superionic H2O and NH3 has been thought as an explanation to stabilize such nonconvective regions. However, a lack of experimental data on the physical properties of those superionic phases has prevented the clarification of this matter. Here, our Brillouin measurements for NH3 show a two-stage reduction in longitudinal wave velocity (V p) by ∼9% and ∼20% relative to the molecular solid in the temperature range of 1,500 K and 2,000 K above 47 GPa. While the first V p reduction observed at the boundary to the superionic α phase was most likely due to the onset of the hydrogen diffusion, the further one was likely attributed to the transition to another superionic phase, denoted γ phase, exhibiting the higher diffusivity. The reduction rate of V p in the superionic γ phase, comparable to that of the liquid, implies that this phase elastically behaves almost like a liquid. Our measurements show that superionic NH3 becomes convective and cannot contribute to the internal stratification.

Experimental evidence for silica-enriched Earth's lower mantle with ferrous iron dominant bridgmanite.

Determination of the chemical composition of the Earth's mantle is of prime importance to understand the evolution, dynamics, and origin of the Earth. However, there is a lack of experimental data on sound velocity of iron-bearing Bridgmanite (Brd) under relevant high-pressure conditions of the whole mantle, which prevents constraints on the mineralogical model of the lower mantle. To uncover these issues, we have conducted sound-velocity measurement of iron-bearing Brd in a diamond-anvil cell (DAC) up to 124 GPa using Brillouin scattering spectroscopy. Here we show that the sound velocities of iron-bearing Brd throughout the whole pressure range of lower mantle exhibit an apparent linear reduction with the iron content. Our data fit remarkably with the seismic structure throughout the lower mantle with Fe2+-enriched Brd, indicating that the greater part of the lower mantle could be occupied by Fe2+-enriched Brd. Our lower-mantle model shows a distinctive Si-enriched composition with Mg/Si of 1.14 relative to the upper mantle (Mg/Si = 1.25), which implies that the mantle convection has been inefficient enough to chemically homogenize the Earth's whole mantle.

Water makes glass elastically stiffer under high-pressure.

Because of its potentially broad industrial applications, a new synthesis of elastically stiffer and stronger glass has been a long standing interest in material science. Various chemical composition and synthesis condition have so far been extensively tested to meet this requirement. Since hydration of matter, in general, significantly reduces its stiffness, it has long been believed that an anhydrous condition has to be strictly complied in synthesis processes. Here we report elastic wave velocities of hydrous SiO2 glass determined in-situ up to ultrahigh-pressures of ~180 gigapascals, revealing that the elastic wave velocities of hydrous glass unexpectedly show the rapid increase with pressure and eventually become greater than those of anhydrous glass above ~15 gigapascals. Furthermore, anomalous change in the velocity gradient at ~100 gigapascals, probably caused by the change in Si-O coordination number from 6 to 6+, was also found at ~40 gigapascals lower pressure condition than that previously reported in anhydrous silica glass, implying that water is a highly effective impurity to make SiO2 glass much denser. This experimental discovery strongly indicates that hydration combined with pressurization is highly effective to synthesize elastically stiffer glass materials, which offers a new insight into the fabrication of industrially useful novel materials.

High-pressure radiative conductivity of dense silicate glasses with potential implications for dark magmas.

The possible presence of dense magmas at Earth's core-mantle boundary is expected to substantially affect the dynamics and thermal evolution of Earth's interior. However, the thermal transport properties of silicate melts under relevant high-pressure conditions are poorly understood. Here we report in situ high-pressure optical absorption and synchrotron Mössbauer spectroscopic measurements of iron-enriched dense silicate glasses, as laboratory analogues for dense magmas, up to pressures of 85 GPa. Our results reveal a significant increase in absorption coefficients, by almost one order of magnitude with increasing pressure to ~50 GPa, most likely owing to gradual changes in electronic structure. This suggests that the radiative thermal conductivity of dense silicate melts may decrease with pressure and so may be significantly smaller than previously expected under core-mantle boundary conditions. Such dark magmas heterogeneously distributed in the lower mantle would result in significant lateral heterogeneity of heat flux through the core-mantle boundary.

A perovskitic lower mantle inferred from high-pressure, high-temperature sound velocity data.

The determination of the chemical composition of Earth's lower mantle is a long-standing challenge in earth science. Accurate knowledge of sound velocities in the lower-mantle minerals under relevant high-pressure, high-temperature conditions is essential in constraining the mineralogy and chemical composition using seismological observations, but previous acoustic measurements were limited to a range of low pressures and temperatures. Here we determine the shear-wave velocities for silicate perovskite and ferropericlase under the pressure and temperature conditions of the deep lower mantle using Brillouin scattering spectroscopy. The mineralogical model that provides the best fit to a global seismic velocity profile indicates that perovskite constitutes more than 93 per cent by volume of the lower mantle, which is a much higher proportion than that predicted by the conventional peridotitic mantle model. It suggests that the lower mantle is enriched in silicon relative to the upper mantle, which is consistent with the chondritic Earth model. Such chemical stratification implies layered-mantle convection with limited mass transport between the upper and the lower mantle.

Evidence of denser MgSiO3 glass above 133 gigapascal (GPa) and implications for remnants of ultradense silicate melt from a deep magma ocean.

Ultralow velocity zones are the largest seismic anomalies in the mantle, with 10-30% seismic velocity reduction observed in thin layers less than 20-40 km thick, just above the Earth's core-mantle boundary (CMB). The presence of silicate melts, possibly a remnant of a deep magma ocean in the early Earth, have been proposed to explain ultralow velocity zones. It is, however, still an open question as to whether such silicate melts are gravitationally stable at the pressure conditions above the CMB. Fe enrichment is usually invoked to explain why melts would remain at the CMB, but this has not been substantiated experimentally. Here we report in situ high-pressure acoustic velocity measurements that suggest a new transformation to a denser structure of MgSiO(3) glass at pressures close to those of the CMB. The result suggests that MgSiO(3) melt is likely to become denser than crystalline MgSiO(3) above the CMB. The presence of negatively buoyant and gravitationally stable silicate melts at the bottom of the mantle, would provide a mechanism for observed ultralow seismic velocities above the CMB without enrichment of Fe in the melt. An ultradense melt phase and its geochemical inventory would be isolated from overlying convective flow over geologic time.

Spectroscopic evidence for ultrahigh-pressure polymorphism in SiO2 glass.

Acoustic wave velocities of SiO2 glass were measured up to pressures of 207 GPa using newly developed Brillouin scattering spectroscopic techniques to address the nature of pressure-induced structural changes. The acoustic wave velocity data suggests three distinct pressure regimes, two of which correspond to changes in the Si-O coordination number with pressure, and one of which indicates the stability of sixfold-coordinated Si over a broad pressure interval from approximately 40-140 GPa. An anomalous increase in the effect of pressure on velocity at 140 GPa most likely corresponds to the onset of structural densification associated with an increase in coordination number from sixfold to a higher coordination state.

Post-perovskite phase transition in MgSiO3.

In situ x-ray diffraction measurements of MgSiO3 were performed at high pressure and temperature similar to the conditions at Earth's core-mantle boundary. Results demonstrate that MgSiO3 perovskite transforms to a new high-pressure form with stacked SiO6-octahedral sheet structure above 125 gigapascals and 2500 kelvin (2700-kilometer depth near the base of the mantle) with an increase in density of 1.0 to 1.2%. The origin of the D" seismic discontinuity may be attributed to this post-perovskite phase transition. The new phase may have large elastic anisotropy and develop preferred orientation with platy crystal shape in the shear flow that can cause strong seismic anisotropy below the D" discontinuity.

Water in Earth's lower mantle.

Secondary ion mass spectrometry measurements show that Earth's representative lower mantle minerals synthesized in a natural peridotitic composition can dissolve considerable amounts of hydrogen. Both MgSiO3-rich perovskite and magnesiowüstite contain about 0.2 weight percent (wt%) H2O, and CaSiO3-rich perovskite contains about 0.4 wt% H2O. The OH absorption bands in Mg-perovskite and magnesiowüstite were also confirmed with the use of infrared microspectroscopic measurements. Earth's lower mantle may store about five times more H2O than the oceans.