Jun Abe

Pressure-induced polymerization (PIP) of aromatic molecules has emerged as an effective method for synthesizing various carbon-based materials. The selection of suitable functionalized molecular precursors is crucial for obtaining the desired structures and functions. In this work, 1,4-difluorobenzene (1,4-DFB) was selected as the building block for PIP. In situ high-pressure investigations of 1,4-DFB reveal a phase transition at approximately 12.0 GPa and an irreversible chemical reaction at 18.7 GPa. Structural analysis of the product and the kinetics of the reaction uncovered the formation of pseudo-hexagonal stacked fluoro-diamond nanothreads with linear growth. Compared to the crystal structure of benzene under high pressure, 1,4-DFB exhibits higher compression along the [001] axis. The anisotropic compression is attributed to the stronger H⋯π interactions along the [01] axis and the potential compression-inhibiting H⋯F interactions along the [100] and [010] axes, and it facilitates a possible reaction pathway along the [01] axis. This work emphasizes the crucial role of functionalization in modulating molecular stacking and influencing the reaction pathway.

A high-temperature high-pressure cell equipped with a metallic window was developed for small-angle neutron scattering (SANS). The feasibility of a Ti alloy (Ti–6Al–4V) as a candidate window material was assessed, considering its mechanical strength and neutron characteristics. SANS experiments should be conducted using safe and reliable materials without risk of window damage or leakage of the activated samples due to window breakage. SANS profiles measured for supercritical heavy water showed maximum scattering intensity at temperatures and pressures near the critical density. Additionally, the utility of the cell for observations of the decomposition of plastic in supercritical water is presented. The cell facilitates analysis of reaction mechanisms under sub- and supercritical conditions, which could provide detailed information to aid efficient decomposition and recycling, contributing to a sustainable society.

We have performed in situ time‐of‐flight neutron diffraction experiments to examine the uptake of deuterium in iron monosulfide at pressures up to 11.4 GPa and temperatures to 1300 K. A D₂ fluid was formed in the experiments through the decomposition of ND₃BD₃, resulting in an oxygen fugacity of approximately 1.2 log units below the iron‐wüstite buffer. Deuterium positions and site occupancies were determined in FeS V, using Rietveld refinements of the powder neutron diffraction patterns. Our structural model indicates that two normally unoccupied sites in the P6₃/mmc FeS V structure, at Wyckoff positions 6h and 4f, are partially occupied by D atoms, with the latter being more dominant. The deuterium content D_x in FeSD_X increases with both pressure and temperature over the experimental conditions explored, from 0.126 (14) at 2.3 GPa and 787 K to 1.20 (16) at 9.7 GPa and 1300 K. The unit‐cell volume expansion per deuterium atom is 1.53 ± 0.16 ų at 6.9 GPa and 960 K, which is smaller than that determined for metallic iron phases at similar conditions. The variation in unit‐cell volume indicates that most deuterium is lost from FeS V upon temperature quenching at high‐pressures. By fitting the obtained FeS V deuterium site occupancies to a thermodynamic model, estimates for the hydrogen contents of iron monosulfide at conditions and oxygen fugacities consistent with the base of the cratonic lithosphere can be made. This results in values in the range of 1,700–2,700 ppm, which contribute to approximately 2–3 ppm hydrogen in the bulk mantle.

This study developed a high-temperature and high-pressure (HTHP) cell for in situ neutron imaging of hydrothermal reactions. The cell’s maximum temperature and pressure were 500 °C and 50 MPa, respectively, and its vessel for observing reactions comprised SUS316 stainless steel. Neutron transmission images were obtained to observe the behavior of sub- and supercritical water and the decomposition of two plastics (polypropylene and polyethylene) at HTHP. The images showed that water’s density and phase changed with temperature and pressure, affecting neutron transmission (and thus image brightness). The plastics began to melt and change shape at 150–200 °C, and they decomposed at 500 °C and 20 MPa. This study provides a basis for future research using the HTHP cell to examine various reactions such as the decomposition of biomass samples, the reforming of heavy oil, and the synthesis of nano-materials using sub- and supercritical water.

Ice polymorphs show extraordinary structural diversity depending on pressure and temperature. The behavior of hydrogen-bond disorder not only is a key ingredient for their structural diversity but also controls their physical properties. However, it has been a challenge to determine the details of the disordered structure in ice polymorphs under pressure, because of the limited observable reciprocal space and inaccuracies related to high-pressure techniques. Here, we present an elucidation of the disordered structure of ice VII, the dominant high-pressure form of water, at 2.2 GPa and 298 K, from both single-crystal and powder neutron-diffraction techniques. We reveal the three-dimensional atomic distributions from the maximum entropy method and unexpectedly find a ring-like distribution of hydrogen in contrast to the commonly accepted discrete sites. In addition, total scattering analysis at 274 K clarified the difference in the intermolecular structure from ice VIII, the ordered counterpart of ice VII, despite an identical molecular geometry. Our complementary structure analyses robustly demonstrate the unique disordered structure of ice VII. Furthermore, these findings are related to proton dynamics, which drastically vary with pressure, and will contribute to an understanding of the structural origin of anomalous physical properties of ice VII under pressures.

Underground engineering for processes such as geological disposal of high-level nuclear waste, CO₂ capture and storage, and mining and drilling for resources requires an understanding of the mechanical behavior of rocks at subsurface stress states, i.e., triaxial compressive stress. Strain measurement using neutron diffraction can be applied to rocks to analyze strain accumulation mechanisms at the microscopic scale. This study reports the development of triaxial compressive apparatus for strain measurement using neutron diffraction. The apparatus can analyze rock specimens (diameter, 25 mm; length, 50 mm) and apply a maximum confining pressure of 50 MPa. Materials for the components of the apparatus were investigated theoretically based on neutron beam transmission and experimentally using neutron diffraction experiments. The feasibility of the apparatus was verified by measuring strain at hydrostatic pressure under the application of confining pressure and triaxial compression. The theoretical and experimental results show that the apparatus could obtain sufficient neutron statistics from a rock specimen. It was confirmed experimentally that the measured strain values are correlated with the applied confining pressure and stress. The lattice strains of quartz minerals measured by neutron diffraction showed linear deformation behavior, indicating that elastic strain accumulated in the minerals. This apparatus will enable the finding of new insights into the deformation mechanisms of rocks.

We applied Kawai-type multi-anvil assemblies (MA6-8) for time-of-flight neutron-diffraction experiments to achieve high-pressures and high-temperatures simultaneously. To achieve sufficient signal intensities, the angular access to the sample was enlarged using slits and tapers on the first-stage anvils. Using SiC-binder sintered diamond for the second-stage anvils that transmits neutrons, sufficient signal intensities were achieved at a high-pressure of ∼23.1 GPa. A high-temperature experiment was also conducted at 16.2 GPa and 973 K, validating the use of tungsten carbide for the second-stage anvils. The present study reveals the capability of the MA6-8 cells in neutron-diffraction experiments to attain pressures and temperatures beyond the limits of the conventional MA6-6 cells used in the high-pressure neutron diffractometer PLANET at the MLF, J-PARC.