Tony Yu

Atomistic insight into viscosity and density of silicate melts under pressure

A defining characteristic of silicate melts is the degree of polymerization (tetrahedral connectivity), which dictates viscosity and affects compressibility. While viscosity of depolymerized silicate melts increases with pressure consistent with the free-volume theory, isothermal viscosity of polymerized melts decreases with pressure up to ~3-5 GPa, above which it turns over to normal (positive) pressure dependence. Here we show that the viscosity turnover in polymerized liquids corresponds to the tetrahedral packing limit, below which the structure is compressed through tightening of the inter-tetrahedral bond angle, resulting in high compressibility, continual breakup of tetrahedral connectivity and viscosity decrease with increasing pressure. Above the turnover pressure, silicon and aluminium coordination increases to allow further packing, with increasing viscosity and density. These structural responses prescribe the distribution of melt viscosity and density with depth and play an important role in magma transport in terrestrial planetary interiors.

High-pressure x-ray diffraction studies on the structure of liquid silicate using a Paris-Edinburgh type large volume press

An experimental setup for high-pressure liquid structure studies with synchrotron x-ray diffraction using the Paris-Edinburgh press has been installed at station 16-BM-B (HPCAT) of the Advanced Photon Source, Argonne National Laboratory. By collecting energy-dispersive data with a synchrotron white beam at various 2θ angles, the present device allows us to obtain the structure factor, S(Q), over a wide range of Q ( = 4πsinθ∕λ) owing to the excellent angular accessibility up to 37° in 2θ and high energy photons well beyond 100 keV. We have successfully collected XRD data on silicate (albite, NaAlSi(3)O(8)) liquids with Q up to ∼22 Å(-1) and pressure up to 5.3 GPa and temperature 1873 K, and obtained the radial distribution function, G(r), with a reasonable resolution. The T-O bond length (where T = Al, Si), which is a fundamental measure of local structure for aluminous silicate consisting of SiO(n) and AlO(n) polyhedra (tetrahedra at 1 atm condition), was found to be slightly shortened to 1.626 Å compared to that of glass at 1 atm. The T-O-T bound angle, which is the linkage of the above polyhedra, is the most responsible for densification. The T-O-T peak in G(r) splits into two peaks, suggesting a differentiation of the bond angle at high-pressure. The present technical development demonstrates that the Paris-Edinburgh press is suitable for studies of silicate liquids under high-pressure conditions.

Experimental evidence supports mantle partial melting in the asthenosphere.

Based on sound velocity measurements, upper mantle seismic anomalies could be explained by a melt fraction as low as 0.2%. The low-velocity zone (LVZ) is a persistent seismic feature in a broad range of geological contexts. It coincides in depth with the asthenosphere, a mantle region of lowered viscosity that may be essential to enabling plate motions. The LVZ has been proposed to originate from either partial melting or a change in the rheological properties of solid mantle minerals. The two scenarios imply drastically distinct physical and geochemical states, leading to fundamentally different conclusions on the dynamics of plate tectonics. We report in situ ultrasonic velocity measurements on a series of partially molten samples, composed of mixtures of olivine plus 0.1 to 4.0 volume % of basalt, under conditions relevant to the LVZ. Our measurements provide direct compressional (VP) and shear (VS) wave velocities and constrain attenuation as a function of melt fraction. Mantle partial melting appears to be a viable origin for the LVZ, for melt fractions as low as ~0.2%. In contrast, the presence of volatile elements appears necessary to explaining the extremely high VP/VS values observed in some local areas. The presence of melt in LVZ could play a major role in the dynamics of plate tectonics, favoring the decoupling of the plate relative to the asthenosphere.

Studies of Local and Intermediate Range Structure in Crystalline and Amorphous Materials at High Pressure Using High-Energy X-rays

The method of high-energy total elastic X-ray scattering to determine the atomic structure of nanocrystalline, highly disordered, and amorphous materials is presented. The current state of the technique, its potential, and limitations are discussed with two successful studies on the pressure induced phase transition in mackinawite (FeS) and the high-pressure behavior of liquid gallium.

Structure of jadeite melt at high pressures up to 4.9 GPa

The structure of jadeite (NaAlSi2O6) melts has been studied using multiple-angle energy-dispersive x-ray diffraction up to 4.9 GPa and 1923 K. The first sharp diffraction peak in the structure factor shifts toward higher momentum transfer as pressure increases, indicating the shrinkage of the intermediate network in the melt. The radial distribution function shows a monotonous decrease in average T-T length and T-O-T angle with increasing pressure, but displays no detectable change in the average bond length between tetrahedrally coordinated cations and oxygen (T-O length, where T = Si4+, Al3+). Our observations indicate that the dominant structural changes occur in the intermediate range order at pressures up to 4.9 GPa. The changes in T-O length, T-T length, and T-O-T angle appear to correlate with the viscosity anomaly in this pressure range.

Combined ultrasonic elastic wave velocity and microtomography measurements at high pressures

Combined ultrasonic and microtomographic measurements were conducted for simultaneous determination of elastic property and density of noncrystalline materials at high pressures. A Paris-Edinburgh anvil cell was placed in a rotation apparatus, which enabled us to take a series of x-ray radiography images under pressure over a 180° angle range and construct accurately the three-dimensional sample volume using microtomography. In addition, ultrasonic elastic wave velocity measurements were carried out simultaneously using the pulse reflection method with a 10° Y-cut LiNbO(3) transducer attached to the end of the lower anvil. Combined ultrasonic and microtomographic measurements were carried out for SiO(2) glass up to 2.6 GPa and room temperature. A decrease in elastic wave velocities of the SiO(2) glass was observed with increasing pressure, in agreement with previous studies. The simultaneous measurements on elastic wave velocities and density allowed us to derive bulk (K(s)) and shear (G) moduli as a function of pressure. K(s) and G of the SiO(2) glass also decreased with increasing pressure. The negative pressure dependence of K(s) is stronger than that of G, and as a result the value of K(s) became similar to G at 2.0-2.6 GPa. There is no reason why we cannot apply this new technique to high temperatures as well. Hence the results demonstrate that the combined ultrasonic and microtomography technique is a powerful tool to derive advanced (accurate) P-V-K(s)-G-(T) equations of state for noncrystalline materials.

Discovery of a Superconducting Cu–Bi Intermetallic Compound by High‐Pressure Synthesis

A new intermetallic compound, the first to be structurally identified in the Cu-Bi binary system, is reported. This compound is accessed by high-pressure reaction of the elements. Its detailed characterization, physical property measurements, and ab initio calculations are described. The commensurate crystal structure of Cu11 Bi7 is a unique variation of the NiAs structure type. Temperature-dependent electrical resistivity and heat capacity measurements reveal a bulk superconducting transition at Tc =1.36 K. Density functional theory calculations further demonstrate that Cu11 Bi7 can be stabilized (relative to decomposition into the elements) at high pressure and temperature. These results highlight the ability of high-pressure syntheses to allow for inroads into heretofore-undiscovered intermetallic systems for which no thermodynamically stable binaries are known.

Ultrahard stitching of nanotwinned diamond and cubic boron nitride in C2-BN composite

Materials combining the hardness and strength of diamond with the higher thermal stability of cubic boron nitride (cBN) have broad potential value in science and engineering. Reacting nanodiamond with cBN at moderate pressures and high temperatures provides a pathway to such materials. Here we report the fabrication of Cx-BN nanocomposites, measuring up to 10 mm in longest dimension, by reacting nanodiamond with pre-synthesized cBN in a large-volume press. The nanocomposites consist of randomly-oriented diamond and cBN domains stitched together by sp3-hybridized C-B and C-N bonds, leading to p-type semiconductivity. Dislocations near the sutures accommodate lattice mismatch between diamond and cBN. Nanotwinning within both diamond and cBN domains further contributes to a bulk hardness ~50% higher than sintered cBN. The nanocomposite of C2-BN exhibits p-type semiconductivity with low activation energy and high thermal stability, making it a functional, ultrahard substance.

A laboratory nanoseismological study on deep-focus earthquake micromechanics

Nanoseismological analyses on labquakes under controlled conditions shed new lights on mechanisms of deep-focus earthquakes. Global earthquake occurring rate displays an exponential decay down to ~300 km and then peaks around 550 to 600 km before terminating abruptly near 700 km. How fractures initiate, nucleate, and propagate at these depths remains one of the greatest puzzles in earth science, as increasing pressure inhibits fracture propagation. We report nanoseismological analysis on high-resolution acoustic emission (AE) records obtained during ruptures triggered by partial transformation from olivine to spinel in Mg2GeO4, an analog to the dominant mineral (Mg,Fe)2SiO4 olivine in the upper mantle, using state-of-the-art seismological techniques, in the laboratory. AEs’ focal mechanisms, as well as their distribution in both space and time during deformation, are carefully analyzed. Microstructure analysis shows that AEs are produced by the dynamic propagation of shear bands consisting of nanograined spinel. These nanoshear bands have a near constant thickness (~100 nm) but varying lengths and self-organize during deformation. This precursory seismic process leads to ultimate macroscopic failure of the samples. Several source parameters of AE events were extracted from the recorded waveforms, allowing close tracking of event initiation, clustering, and propagation throughout the deformation/transformation process. AEs follow the Gutenberg-Richter statistics with a well-defined b value of 1.5 over three orders of moment magnitudes, suggesting that laboratory failure processes are self-affine. The seismic relation between magnitude and rupture area correctly predicts AE magnitude at millimeter scales. A rupture propagation model based on strain localization theory is proposed. Future numerical analyses may help resolve scaling issues between laboratory AE events and deep-focus earthquakes.

The effects of shear deformation on planetesimal core segregation: Results from in-situ X-ray micro-tomography

Abstract It is well accepted that the Earth formed by the accretion and collision of small (10–100 km), rocky bodies called planetesimals. W-Hf isotopic evidence from meteorites suggest that the cores of many planetesimals formed within a relatively short time frame of ~3 My. While a very hot, deep magma ocean is generally thought to have been the driving mechanism for core formation in large planetary bodies, it inadequately explains differentiation and core formation in small planetesimals due to temperatures potentially being insufficient for wide-scale silicate melting to occur. In order for these planetesimals to differentiate within such a relatively short time without a magma ocean, a critical melt volume of the metallic (core-forming) phase and sufficient melt connectivity and grain size must have existed to attain the required permeability and lead to efficient core formation. Shear deformation may increase the connectedness of melt and the permeability, and thus could have been a major contributing factor in the formation of planetesimal cores. This deformation may have been caused by large impacts and collisions experienced by the planetesimals in the early solar system. The purpose of this work is to test the hypothesis that shear deformation enhances the connectivity and permeability of Fe-S melt within a solid silicate (olivine) matrix, such that rapid core formation is plausible. A rotational Drickamer apparatus (RDA) was used to heat and torsionally deform a sample of solid olivine + FeS liquid through six steps of large-strain shear deformation. After each deformation step, X-ray microtomographs were collected in the RDA to obtain in situ three-dimensional images of the sample. The resulting digital volumes were processed and permeability simulations utilizing the lattice Boltzmann method were performed to determine the effect of shear deformation on connectivity and permeability within the sample. The resulting permeabilities of the sample at various steps of deformation are the same within uncertainty and do not exhibit a change with increasing deformation. Additionally, the migration velocity calculated from the permeability of the sample is not high enough for segregation to take place within the time frame of ~3 My. In addition to further constraining the mechanism of core formation in planetesimals, the image processing techniques developed in this study will be of great benefit to future studies utilizing similar methods.