Toughening oxide glasses through paracrystallization.

Glasses, unlike crystals, are intrinsically brittle due to the absence of microstructure-controlled toughening, creating fundamental constraints for their technological applications. Consequently, strategies for toughening glasses without compromising their other advantageous properties have been long sought after but elusive. Here we report exceptional toughening in oxide glasses via paracrystallization, using aluminosilicate glass as an example. By combining experiments and computational modelling, we demonstrate the uniform formation of crystal-like medium-range order clusters pervading the glass structure as a result of paracrystallization under high-pressure and high-temperature conditions. The paracrystalline oxide glasses display superior toughness, reaching up to 1.99 ± 0.06 MPa m1/2, surpassing any other reported bulk oxide glasses, to the best of our knowledge. We attribute this exceptional toughening to the excitation of multiple shear bands caused by a stress-induced inverse transformation from the paracrystalline to amorphous states, revealing plastic deformation characteristics. This discovery presents a potent strategy for designing highly damage-tolerant glass materials and emphasizes the substantial influence of atomic-level structural variation on the properties of oxide glasses.

Variation in bridgmanite grain size accounts for the mid-mantle viscosity jump.

A viscosity jump of one to two orders of magnitude in the lower mantle of Earth at 800-1,200-km depth is inferred from geoid inversions and slab-subducting speeds. This jump is known as the mid-mantle viscosity jump1,2. The mid-mantle viscosity jump is a key component of lower-mantle dynamics and evolution because it decelerates slab subduction3, accelerates plume ascent4 and inhibits chemical mixing5. However, because phase transitions of the main lower-mantle minerals do not occur at this depth, the origin of the viscosity jump remains unknown. Here we show that bridgmanite-enriched rocks in the deep lower mantle have a grain size that is more than one order of magnitude larger and a viscosity that is at least one order of magnitude higher than those of the overlying pyrolitic rocks. This contrast is sufficient to explain the mid-mantle viscosity jump1,2. The rapid growth in bridgmanite-enriched rocks at the early stage of the history of Earth and the resulting high viscosity account for their preservation against mantle convection5-7. The high Mg:Si ratio of the upper mantle relative to chondrites8, the anomalous 142Nd:144Nd, 182W:184W and 3He:4He isotopic ratios in hot-spot magmas9,10, the plume deflection4 and slab stagnation in the mid-mantle3 as well as the sparse observations of seismic anisotropy11,12 can be explained by the long-term preservation of bridgmanite-enriched rocks in the deep lower mantle as promoted by their fast grain growth.

Superhydrous aluminous silica phases as major water hosts in high-temperature lower mantle.

Water transported by subducted oceanic plates changes mineral and rock properties at high pressures and temperatures, affecting the dynamics and evolution of the Earth's interior. Although geochemical observations imply that water should be stored in the lower mantle, the limited amounts of water incorporation in pyrolitic lower-mantle minerals suggest that water in the lower mantle may be stored in the basaltic fragments of subducted slabs. Here, we performed multianvil experiments to investigate the stability and water solubility of aluminous stishovite and CaCl2-structured silica, referred to as poststishovite, in the SiO2-Al2O3-H2O systems at 24 to 28 GPa and 1,000 to 2,000 °C, representing the pressure-temperature conditions of cold subducting slabs to hot upwelling plumes in the top lower mantle. The results indicate that both alumina and water contents in these silica minerals increase with increasing temperature under hydrous conditions due to the strong Al3+-H+ charge coupling substitution, resulting in the storage of water up to 1.1 wt %. The increase of water solubility in these hydrous aluminous silica phases at high temperatures is opposite of that of other nominally anhydrous minerals and of the stability of the hydrous minerals. This feature prevents the releasing of water from the subducting slabs and enhances the transport water into the deep lower mantle, allowing significant amounts of water storage in the high-temperature lower mantle and circulating water between the upper mantle and the lower mantle through subduction and plume upwelling. The shallower depths of midmantle seismic scatterers than expected from the pure SiO2 stishovite-poststishovite transition pressure support this scenario.

Novel Class of Rhenium Borides Based on Hexagonal Boron Networks Interconnected by Short B2 Dumbbells.

Transition metal borides are known due to their attractive mechanical, electronic, refractive, and other properties. A new class of rhenium borides was identified by synchrotron single-crystal X-ray diffraction experiments in laser-heated diamond anvil cells between 26 and 75 GPa. Recoverable to ambient conditions, compounds rhenium triboride (ReB3) and rhenium tetraboride (ReB4) consist of close-packed single layers of rhenium atoms alternating with boron networks built from puckered hexagonal layers, which link short bonded (∼1.7 Å) axially oriented B2 dumbbells. The short and incompressible Re-B and B-B bonds oriented along the hexagonal c-axis contribute to low axial compressibility comparable with the linear compressibility of diamond. Sub-millimeter samples of ReB3 and ReB4 were synthesized in a large-volume press at pressures as low as 33 GPa and used for material characterization. Crystals of both compounds are metallic and hard (Vickers hardness, H V = 34(3) GPa). Geometrical, crystal-chemical, and theoretical analysis considerations suggest that potential ReB x compounds with x > 4 can be based on the same principle of structural organization as in ReB3 and ReB4 and possess similar mechanical and electronic properties.

Crustal melting in orogenic belts revealed by eclogite thermal properties.

Partial melting in the continental crust may play a critical role on the behavior of continents during collision. However, the occurrence of partial melt in orogenic continental crust is not well understood. Since the temperature of the orogen is controlled by the thermal properties of constituent rocks, we measured the thermal conductivity and diffusivity of eclogite, the most important ultrahigh pressure metamorphic rocks, as a function of pressure, temperature, composition, and water content, and simulated the thermal structure of the Sulu and Himalaya-Tibet orogens in eastern and southwestern China, respectively. Our results show that the temperature at ~30-km depth beneath the orogens reaches the solidus of wet granite and phengite (~940 K), therefore, the partial melting in the orogenic continental crust is well explained. The melt may facilitate the exhumation of subducted crust, produce the low seismic-velocity zone, and cause the high-conductivity anomaly in the shallow depth of orogenic belts.

A simplified rapid-quench multi-anvil technique.

We report a new rapid-quench technique for the Kawai-type multi-anvil press: several important improvements were made to our previous design. As a result, we are able to routinely quench melts with low glass-forming ability and form glasses. Owing to the use of 3D-printed parts to supply the coolant, the new design is easier to assemble and demonstrates better temperature stability and cooling rate. It was also found that the cooling rate is both pressure- and temperature-dependent. The cooling rate increases with increasing pressure from 6700 °C/s at 1 GPa to 8200 °C/s at 5.5 GPa and decreases with increasing temperature at a rate of 550 °C s-1/100 °C. Taking these dependencies into account, the new rapid-quench design produces more than 15% higher cooling rate compared to the previous design. Moreover, enhancing coolant circulation, which was achieved by using tapered inner anvils with holes, additionally increases the cooling rate by about 4%. As the structure of the rapid-quench assembly differs dramatically from other existing designs, pressure calibration and temperature distribution in the experimental cell and sample capsule were determined for the first time. It was found that the first 0.6 MN of press load is not used to generate pressure due to the hard tungsten components in the assembly. At the current state-of-the-art, it is possible to routinely reach a pressure of 9 GPa and a temperature of 2200 K with the temperature variation not exceeding 70 K within the sample capsule.

Synthesis of paracrystalline diamond.

Solids in nature can be generally classified into crystalline and non-crystalline states1-7, depending on whether long-range lattice periodicity is present in the material. The differentiation of the two states, however, could face fundamental challenges if the degree of long-range order in crystals is significantly reduced. Here we report a paracrystalline state of diamond that is distinct from either crystalline or amorphous diamond8-10. The paracrystalline diamond reported in this work, consisting of sub-nanometre-sized paracrystallites that possess a well-defined crystalline medium-range order up to a few atomic shells4,5,11-13, was synthesized in high-pressure high-temperature conditions (for example, 30 GPa and 1,600 K) employing face-centred cubic C60 as a precursor. The structural characteristics of the paracrystalline diamond were identified through a combination of X-ray diffraction, high-resolution transmission microscopy and advanced molecular dynamics simulation. The formation of paracrystalline diamond is a result of densely distributed nucleation sites developed in compressed C60 as well as pronounced second-nearest-neighbour short-range order in amorphous diamond due to strong sp3 bonding. The discovery of paracrystalline diamond adds an unusual diamond form to the enriched carbon family14-16, which exhibits distinguishing physical properties and can be furthered exploited to develop new materials. Furthermore, this work reveals the missing link in the length scale between amorphous and crystalline states across the structural landscape, having profound implications for recognizing complex structures arising from amorphous materials.

Asthenosphere dynamics based on the H2O dependence of element diffusivity in olivine.

The oceanic asthenosphere shows two enigmatic features: low viscosity and high electrical conductivity. Their origins gather wide attention, but remain unsolved. Recent self-diffusivity measurements as a function of H2O content in olivine demonstrated that the H2O-incorporation in olivine cannot soften the asthenosphere, but it enhances the ionic conductivity, and causes the high-conductivity anomaly.

A rapid-quench technique for multi-anvil high-pressure-temperature experiments.

In order to extend the pressure and compositional range where silicate melts can be quenched to form glass in a multi-anvil high-pressure and high-temperature apparatus, a rapid-quench technique, which includes an external cooling system and a low thermal-inertia assembly, was developed. This technique allows much higher cooling rates (6000-7000 °C/s) than regular piston-cylinder (130 °C/s) apparatus and multi-anvil (650 °C/s) apparatus, which are widely used in solid Earth science. Such high cooling rates are critical to avoid unwanted changes in a sample, such as melt crystallization and volatile loss, during quenching.

High-pressure synthesis of ultraincompressible hard rhenium nitride pernitride Re2(N2)(N)2 stable at ambient conditions.

High-pressure synthesis in diamond anvil cells can yield unique compounds with advanced properties, but often they are either unrecoverable at ambient conditions or produced in quantity insufficient for properties characterization. Here we report the synthesis of metallic, ultraincompressible (K0 = 428(10) GPa), and very hard (nanoindentation hardness 36.7(8) GPa) rhenium nitride pernitride Re2(N2)(N)2. Unlike known transition metals pernitrides Re2(N2)(N)2 contains both pernitride N24- and discrete N3- anions, which explains its exceptional properties. Re2(N2)(N)2 can be obtained via a reaction between rhenium and nitrogen in a diamond anvil cell at pressures from 40 to 90 GPa and is recoverable at ambient conditions. We develop a route to scale up its synthesis through a reaction between rhenium and ammonium azide, NH4N3, in a large-volume press at 33 GPa. Although metallic bonding is typically seen incompatible with intrinsic hardness, Re2(N2)(N)2 turned to be at a threshold for superhard materials.

Complete agreement of the post-spinel transition with the 660-km seismic discontinuity.

The 660-km seismic discontinuity, which is a significant structure in the Earth's mantle, is generally interpreted as the post-spinel transition, as indicated by the decomposition of ringwoodite to bridgmanite + ferropericlase. All precise high-pressure and high-temperature experiments nevertheless report 0.5-2 GPa lower transition pressures than those expected at the discontinuity depth (i.e. 23.4 GPa). These results are inconsistent with the post-spinel transition hypothesis and, therefore, do not support widely accepted models of mantle composition such as the pyrolite and CI chondrite models. Here, we present new experimental data showing post-spinel transition pressures in complete agreement with the 660-km discontinuity depth obtained by high-resolution in situ X-ray diffraction in a large-volume high-pressure apparatus with a tightly controlled sample pressure. These data affirm the applicability of the prevailing mantle models. We infer that the apparently lower pressures reported by previous studies are experimental artefacts due to the pressure drop upon heating. The present results indicate the necessity of reinvestigating the position of mantle mineral phase boundaries previously obtained by in situ X-ray diffraction in high-pressure-temperature apparatuses.

A nearly water-saturated mantle transition zone inferred from mineral viscosity.

An open question for solid-earth scientists is the amount of water in Earth's interior. The uppermost mantle and lower mantle contain little water because their dominant minerals, olivine and bridgmanite, have limited water storage capacity. In contrast, the mantle transition zone (MTZ) at a depth of 410 to 660 km is considered to be a potential water reservoir because its dominant minerals, wadsleyite and ringwoodite, can contain large amounts of water [up to 3 weight % (wt %)]. However, the actual amount of water in the MTZ is unknown. Given that water incorporated into mantle minerals can lower their viscosity, we evaluate the water content of the MTZ by measuring dislocation mobility, a property that is inversely proportional to viscosity, as a function of temperature and water content in ringwoodite and bridgmanite. We find that dislocation mobility in bridgmanite is faster by two orders of magnitude than in anhydrous ringwoodite but 1.5 orders of magnitude slower than in water-saturated ringwoodite. To fit the observed mantle viscosity profiles, ringwoodite in the MTZ should contain 1 to 2 wt % water. The MTZ should thus be nearly water-saturated globally.

Small effect of water on upper-mantle rheology based on silicon self-diffusion coefficients.

Water has been thought to affect the dynamical processes in the Earth's interior to a great extent. In particular, experimental deformation results suggest that even only a few tens of parts per million of water by weight enhances the creep rates in olivine by orders of magnitude. However, those deformation studies have limitations, such as considering only a limited range of water concentrations and very high stresses, which might affect the results. Rock deformation can also be understood as an effect of silicon self-diffusion, because the creep rates of minerals at temperatures as high as those in the Earth's interior are limited by self-diffusion of the slowest species. Here we experimentally determine the silicon self-diffusion coefficient DSi in forsterite at 8 GPa and 1,600 K to 1,800 K as a function of water content CH2O from less than 1 to about 800 parts per million of water by weight, yielding the relationship, DSi ≈ (CH2O)(1/3). This exponent is strikingly lower than that obtained by deformation experiments (1.2; ref. 7). The high nominal creep rates in the deformation studies under wet conditions may be caused by excess grain boundary water. We conclude that the effect of water on upper-mantle rheology is very small. Hence, the smooth motion of the Earth's tectonic plates cannot be caused by mineral hydration in the asthenosphere. Also, water cannot cause the viscosity minimum zone in the upper mantle. And finally, the dominant mechanism responsible for hotspot immobility cannot be water content differences between their source and surrounding regions.