Joseph M. Zaug

Synthesis and characterization of nitrides of iridium and palladium

We describe the synthesis of nitrides of iridium and palladium using the laser-heated diamond anvil cell. We have used the in situ techniques of x-ray powder diffraction and Raman scattering to characterize these compounds and have compared our experimental findings where possible to the results of first-principles theoretical calculations. We suggest that palladium nitride is isostructural with pyrite, while iridium nitride has a monoclinic symmetry and is isostructural with baddeleyite.

The diamond 13C/12C isotope Raman pressure sensor system for high-temperature/pressure diamond-anvil cells with reactive samples

By using a thin 13C diamond chip together with a 12C diamond chip as sensors, the diamond Raman spectra provide the means to measure pressure precisely (±0.3 GPa) at any temperature (10–1200 K) and simultaneous hydrostatic (or quasihydrostatic) pressure (0–25 GPa) for any sample compatible with an externally heated diamond-anvil cell. Minimum interference between the Raman spectrum from the diamond anvils and those of the pressure sensors is obtained by measuring pressures with the Raman signal from the 13C diamond chip up to 13 GPa, and that from the 12C chip above 10 GPa. The best crystallographic orientation of the diamond anvils is with the [100] direction along the direction of applied force, in order to further minimize the interference. At 298 K, the pressure dependence of the 13C diamond first-order Raman line is given by ν(P)=νRT+aP for 91 at. % 13C diamond, where νRT(13C)=1287.79±0.28 cm−1 and a(13C)=2.83±0.05 cm−1/GPa. Analysis of values from the literature shows that the pressure dependence of...

Pressure-dependent structures of amorphous red phosphorus and the origin of the first sharp diffraction peaks.

Characterizing the nature of medium-range order (MRO) in liquids and disordered solids is important for understanding their structure and transport properties. However, accurately portraying MRO, as manifested by the first sharp diffraction peak (FSDP) in neutron and X-ray scattering measurements, has remained elusive for more than 80 years. Here, using X-ray diffraction of amorphous red phosphorus compressed to 6.30 GPa, supplemented with micro-Raman scattering studies, we build three-dimensional structural models consistent with the diffraction data. We discover that the pressure dependence of the FSDP intensity and line position can be quantitatively accounted for by a characteristic void distribution function, defined in terms of average void size, void spacing and void density. This work provides a template to unambiguously interpret atomic and void-space MRO across a broad range of technologically promising network-forming materials.

Molecular dynamics simulations of HMX crystal polymorphs using a flexible molecule force field

Molecular dynamics simulations using a recently developed quantum chemistry-based atomistic force field [J. Phys. Chem. B, 103 (1999) 3570 ] were performed in order to obtain unit cell parameters, coefficients of thermal expansion, and heats of sublimation for the three pure crystal polymorphs of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The predictions for β-, α-, and δ-HMX showed good agreement with the available experimental data. For the case of β-HMX, anisotropic sound speeds were calculated from the molecular dynamics simulation-predicted elastic coefficients and compared with recent Impulsive Stimulated Light Scattering (ISLS) sound speed measurements. The level of agreement is encouraging.

Optical calibration of pressure sensors for high pressures and temperatures

We present the results of Raman-scattering measurements of diamond (C12) and of cubic boron nitride, and fluorescence measurements of ruby, Sm:yttrium aluminum garnet (Sm:YAG), and SrB4O7:Sm2+ in the diamond anvil cell at high pressures and temperatures. These measurements were accompanied by synchrotron x-ray-diffraction measurements on gold. We have extended the room-temperature calibration of Sm:YAG in a quasihydrostatic regime up to 100 GPa. The ruby scale is found to systematically underestimate pressure at high pressures and temperatures compared with all the other sensors. On this basis, we propose an alternative high-temperature ruby pressure scale that is valid to at least 100 GPa and 850 K.

Pressure-dependent decomposition kinetics of the energetic material HMX up to 3.6 GPa.

The effect of pressure on the global thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Global decomposition rates were determined by fitting the fraction reacted to the extended-Prout-Tompkins nucleation-growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low-to-moderate pressures (i.e., between ambient pressure and 0.1 GPa) and decelerates the decomposition at higher pressures. The decomposition acceleration is attributed to pressure-enhanced autocatalysis, whereas the deceleration at high pressures is attributed to pressure-inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both the beta- and delta-polymorphs of HMX are sensitive to pressure in the thermally induced decomposition kinetics.

Impulsive stimulated light scattering from opaque materials at high pressure

Recent progress in the application of impulsive stimulated light scattering to opaque materials under high pressure is reviewed. Measured elastic constants and sound velocities of polycrystalline hcp e-iron to 115 GPa are presented.

Synthesis and characterization of a nanocrystalline diamond aerogel

Aerogel materials have myriad scientific and technological applications due to their large intrinsic surface areas and ultralow densities. However, creating a nanodiamond aerogel matrix has remained an outstanding and intriguing challenge. Here we report the high-pressure, high-temperature synthesis of a diamond aerogel from an amorphous carbon aerogel precursor using a laser-heated diamond anvil cell. Neon is used as a chemically inert, near-hydrostatic pressure medium that prevents collapse of the aerogel under pressure by conformally filling the aerogel’s void volume. Electron and X-ray spectromicroscopy confirm the aerogel morphology and composition of the nanodiamond matrix. Time-resolved photoluminescence measurements of recovered material reveal the formation of both nitrogen- and silicon- vacancy point-defects, suggesting a broad range of applications for this nanocrystalline diamond aerogel.

Ultrafast observation of shocked states in a precompressed material

We apply ultrafast single shot interferometry to determine the pressure and density of argon shocked from up to 7.8 GPa static initial pressure in a diamond anvil cell. This method enables the observation of thermodynamic states distinct from those observed in either single shock or isothermal compression experiments. In particular, this method enables access to high density, relatively low temperature states of light materials, such as isentropically compressed states of giant planets. Further, since excitation by a shock wave is intrinsically ultrafast and this method has picoseconds time resolution, it has the potential to observe the collective dynamics of materials undergoing shock induced phase transitions and chemistry on ultrafast time scales. We also present a straightforward method for interpreting ultrafast shock wave data which determines the index of refraction at the shock front, and the particle and shock velocities for shock waves in transparent materials. Based on these methods, we observ...

The α→ϵ phase transition in iron at strain rates up to ∼109 s−1

We have used a table-top scale laser to dynamically compress iron at strain rates in excess of 109 s−1. Using an embedded ultrafast interferometer, we have measured corresponding free surface histories with a time resolution of approximately 10 ps. We have analyzed the surface histories using a method that accounts for nonsteady wave propagation and time-dependent material behavior. We show that at these strain rates, the α→ϵ polymorphic transition begins within 100 ps after an initial very large (∼10 GPa) and mostly elastic compression and appears largely complete within a similar time thereafter. The corresponding deviatoric stress before the transition begins can exceed 3 GPa, while the transition stress itself is up to 25 GPa, nearly twice the value measured at low strain rates. We use these results to propose a systematic variation with loading time of the normal-stress/relative-volume curve followed by iron during rapid compression.