Magnetic flux tailoring through Lenz lenses for ultrasmall samples: A new pathway to high-pressure nuclear magnetic resonance

A new pathway to nuclear magnetic resonance (NMR) spectroscopy for picoliter-sized samples (including those kept in harsh and extreme environments, particularly in diamond anvil cells) is introduced, using inductively coupled broadband passive electromagnetic lenses, to locally amplify the magnetic field at the isolated sample, leading to an increase in sensitivity. The lenses are adopted for the geometrical restrictions imposed by a toroidal diamond indenter cell and yield signal-to-noise ratios at pressures as high as 72 GPa at initial sample volumes of only 230 pl. The corresponding levels of detection are found to be up to four orders of magnitude lower compared to formerly used solenoidal microcoils. Two-dimensional nutation experiments on long-chained alkanes, CnH2n+2 (n = 16 to 24), as well as homonuclear correlation spectroscopy on thymine, C5H6N2O2, were used to demonstrate the feasibility of this approach for higher-dimensional NMR experiments, with a spectral resolution of at least 2 parts per million. This approach opens up the field of ultrahigh-pressure sciences to one of the most versatile spectroscopic methods available in a pressure range unprecedented up to now

Prevalence of Pretransition Disordering in the Rutile-to-Cacl2 Phase Transition of Geo2

The ability to tailor a material\u27s electronic properties using density driven disordering has emerged as a powerful route to materials design. The observation of anomalous structural and electronic behavior in the rutile to CaCl2 phase transition in SnO2 led to the prediction that such behavior is inherent to all oxides experiencing such a phase transition sequence [Smith et al., J. Phys. Chem. Lett. 10, 5351 (2019)1948-718510.1021/acs.jpclett.9b01633]. Here, the ultrawide band gap semiconductor GeO2 is confirmed to exhibit anomalous behavior during the rutile to CaCl2 phase transition. A phase pure rutile GeO2 sample synthesized under high-pressure, high-temperature conditions is probed using synchrotron diffraction and x-ray and optical spectroscopy under high pressure conditions. Density functional theory calculations show that the enthalpic barrier to displacing an oxygen along the B1g librational mode decreases with pressure leading up to the rutile to CaCl2 phase transition. The band structure of the distorted state shows that such oxygen displacements form small polarons

Effect of Fe3+ on Phase Relations in the Lower Mantle : Implications for Redox Melting in Stagnant Slabs

Recent studies have revealed that Earth's deep mantle may have a wider range of oxygen fugacities than previously thought. Such a large heterogeneity might be caused by material subducted into the deep mantle. However, high-pressure phase relations are poorly known in systems including Fe3+ at the top of the lower mantle, where the subducted slab may be stagnant. We therefore conducted high-pressure and high-temperature experiments using a multi-anvil apparatus to study the phase relations in a Fe3+-bearing system at 26 GPa and 1573–2073 K, at conditions prevailing at the top of the lower mantle. At temperatures below 1923 K, MgSiO3-rich bridgmanite, an Fe3+-rich oxide phase, and SiO2 coexist in the recovered sample. Quenched partial melt was observed above 1973 K, which is significantly lower than the solidus temperature of an equivalent Fe3+-free bulk composition. The partial melt obtained from the Fe3+-rich bulk composition has a higher iron content than coexisting bridgmanite, similar to the Fe2+-dominant system. The results suggest that strong mantle oxygen fugacity anomalies might alter the subsolidus and melting phase relations under lower mantle conditions. We conclude that (1) a small amount of melt may be generated from an Al-depleted region of a stagnant slab, such as subducted former banded-iron-formation, and (2) Fe3+ is not transported into the deep part of the lower mantle because of its incompatibility during melting

In situ Viscometry of Primitive Lunar Magmas at High Pressure and High Temperature

Understanding the dynamics of the magmatic evolution of the interior of the Moon requires accurate knowledge of the viscosity (η) of lunar magmas at high pressure (P) and high temperature (T) conditions. Although the viscosities of terrestrial magmas are relatively well-documented, and their relation to magma composition well-studied, the viscosities of lunar titano-silicate melts are not well-known. Here, we present an experimentally measured viscosity dataset for three end member compositions, characterized by a wide range of titanium contents, at lunar-relevant pressure-temperature range of ∼1.1–2.4 GPa and 1830–2090 K. In situ viscometry using the falling sphere technique shows that the viscosity of lunar melts varies between ∼0.13 and 0.87 Pa-s depending on temperature, pressure and composition. Viscosity decreases with increasing temperature with activation energies for viscous flow of Ea = 201 kJ/mol and Ea = 106 kJ/mol for low-titanium (Ti) and high-Ti melts, respectively. Pressure is found to mildly increase the viscosity of these intermediate polymerized melts by a factor of ∼1.5 between 1.1 and 2.4 GPa. Viscosities of low-Ti and high-Ti magmas at their respective melting temperatures are very close. However at identical P-T conditions (∼1.3 GPa, ∼1840 K) low-Ti magmas are about a factor of three more viscous than high-Ti magmas, reflecting structural effects of Si and Ti on melt viscosity. Measured viscosities differ significantly from empirical models based on measurements of the viscosity of terrestrial basalts, with largest deviations observed for the most Ti-rich and Si-poor composition. Viscosity coefficients for these primitive lunar melts are found to be lower than those of common terrestrial basalts, giving them a high mobility throughout the lunar mantle and onto the surface of the Moon despite their Fe and Ti-rich compositions

Terapascal static pressure generation with ultrahigh yield strength nanodiamond

Studies of materials’ properties at high and ultrahigh pressures lead to discoveries of unique physical and chemical phenomena and a deeper understanding of matter. In high-pressure research, an achievable static pressure limit is imposed by the strength of available strong materials and design of high-pressure devices. Using a high-pressure and high-temperature technique, we synthesized optically transparent microballs of bulk nanocrystalline diamond, which were found to have an exceptional yield strength (~460 GPa at a confining pressure of ~70 GPa) due to the unique microstructure of bulk nanocrystalline diamond. We used the nanodiamond balls in a double-stage diamond anvil cell high-pressure device that allowed us to generate static pressures beyond 1 TPa, as demonstrated by synchrotron x-ray diffraction. Outstanding mechanical properties (strain-dependent elasticity, very high hardness, and unprecedented yield strength) make the nanodiamond balls a unique device for ultrahigh static pressure generation. Structurally isotropic, homogeneous, and made of a low-Z material, they are promising in the field of x-ray optical applications

Direct tomography imaging for inelastic x-ray scattering experiments at high pressure

A method to separate the non-resonant inelastic X-ray scattering signal of a micro-metric sample contained inside a diamond anvil cell (DAC) from the signal originating from the high-pressure sample environment is described. Especially for high-pressure experiments, the parasitic signal originating from the diamond anvils, the gasket and/or the pressure medium can easily obscure the sample signal or even render the experiment impossible. Another severe complication for high-pressure non-resonant inelastic X-ray measurements, such as X-ray Raman scattering spectroscopy, can be the proximity of the desired sample edge energy to an absorption edge energy of elements constituting the DAC. It is shown that recording the scattered signal in a spatially resolved manner allows these problems to be overcome by separating the sample signal from the spurious scattering of the DAC without constraints on the solid angle of detection. Furthermore, simple machine learning algorithms facilitate finding the corresponding detector pixels that record the sample signal. The outlined experimental technique and data analysis approach are demonstrated by presenting spectra of the Si L-2,L-3-edge and O K-edge of compressed alpha-quartz. The spectra are of unprecedented quality and both the O K-edge and the Si L-2,L-3-edge clearly show the existence of a pressure-induced phase transition between 10 and 24 GPa.Peer reviewe

Chemical analysis of trace elements at the nanoscale in samples recovered from laser-heated diamond anvil cell experiments

Abstract: High pressure and high temperature experiments performed with laser-heated diamond anvil cells (LH-DAC) are being extensively used in geosciences to study matter at conditions prevailing in planetary interiors. Due to the size of the apparatus itself, the samples that are produced are extremely small, on the order of few tens of micrometers. There are several ways to analyze the samples and extract physical, chemical or structural information, using either in situ or ex situ methods. In this paper, we compare two nanoprobe techniques, namely nano-XRF and NanoSIMS, that can be used to analyze recovered samples synthetized in a LH-DAC. With these techniques, it is possible to extract the spatial distribution of chemical elements in the samples. We show the results for several standards and discuss the importance of proper calibration for the acquisition of quantifiable results. We used these two nanoprobe techniques to retrieve elemental ratios of dilute species (few tens of ppm) in quenched experimental molten samples relevant for the formation of the iron-rich core of the Earth. We finally discuss the applications of such probes to constrain the partitioning of trace elements between metal and silicate phases, with a focus on moderately siderophile elements, tungsten and molybdenum