Using powder X‐ray diffraction in conjunction with a diamond anvil cell (DAC), the unit cell volume of triamino‐trinitrobenzene (TATB) has been measured from ambient pressure to 13 GPa. The resultant isotherm is compared with previous theoretical (Byrd and Rice and Pastine and Bernecker) and experimental (Olinger and Cady) works. While all reports are consistent to approximately 2 GPa, our measurements reveal a slightly stiffer TATB material than reported by Olinger and Cady and an intermediate compressibility compared with the isotherms predicted by the two theoretical works. Analysis of the room temperature isotherm using the semi‐empirical, Murnaghan, Birch–Murnaghan, and Vinet equations of state (EOS) provided a determination of the isothermal bulk modulus (Ko) and its pressure‐derivative (Ko′) for TATB. From these fits to our P–V isotherm, from ambient pressure to 8 GPa, the average results for the zero‐pressure bulk modulus and its pressure derivative were found to be 14.7 GPa and 10.1, respectively. For comparison to shock experiments on pressed TATB powder and its plastic‐bonded formulation PBX 9502 (95% TATB, 5% Kel‐F 800), the isotherm was transformed to the pseudo‐velocity Us–up plane using the Rankine–Hugoniot jump conditions. This analysis provides an extrapolated bulk sound speed, co=1.70 km s−1, for TATB and its agreement with a previous determination (co=1.43 km s−1) is discussed. Furthermore, our P–V and corresponding Us–up curves reveal a subtle cusp at approximately 8 GPa. This cusp is discussed in relation to similar observations made for the aromatic hydrocarbons anthracene, benzene and toluene, graphite, and trinitrotoluene (TNT).
The pressure-temperature (P-T) phase diagram of 1,1-diamino-2,2-dinitroethylene (FOX-7) was determined by in situ synchrotron infrared radiation spectroscopy with the resistively heated diamond anvil cell (DAC) technique. The stability of high-P-T FOX-7 polymorphs is established from ambient pressure up to 10 GPa and temperatures until decomposition. The phase diagram indicates two near isobaric phase boundaries at ∼2 GPa (α → I) and ∼5 GPa (I → II) that persists from 25 °C until the onset of decomposition at ∼300 °C. In addition, the ambient pressure, high-temperature α → β phase transition (∼111 °C) lies along a steep boundary (∼100 °C/GPa) with a α-β-δ triple point at ∼1 GPa and 300 °C. A 0.9 GPa isobaric temperature ramping measurement indicates a limited stability range for the γ-phase between 0.5 and 0.9 GPa and 180 and 260 °C, terminating in a β-γ-δ triple point. With increasing pressure, the δ-phase exhibited a small negative dT/dP slope (up to ∼0.2 GPa) before turning over to a positive 70 °C/GPa slope, at higher pressures. The decomposition boundary (∼55 °C/GPa) was identified through the emergence of spectroscopic signatures of the characteristic decomposition products as well as trapped inclusions within the solid KBr pressure media.
The structural phase stability of 1,1-diamino-2,2-dinitroethylene (FOX-7) has been studied up to 10 GPa through isothermal compression at 100 °C and 200 °C using synchrotron mid- and far-infrared spectroscopy. During isothermal compression at 100 °C changes are observed in vibrational spectra with increase in pressure that are indicative of significant distortion to monoclinic α phase or a possible structural transformation to a high pressure α(') phase at 2.2 GPa and α(") phase at 6.1 GPa. At 200 °C, for the far- and mid-IR regimes, the similar changes were observed at 2.1 (2.0) GPa and 5.3 (5.5) GPa, respectively. The observed change is nearly isobaric, consistent with previously reported high pressure and room temperature values, up to the highest temperature of 200 °C reached in our experiments. Over the total P-T range investigated, up to ∼10 GPa and 200 °C, we observed no evidence of sample decomposition. The observed changes are partially reversible with only slight evidence of the high pressure distortion remaining upon complete decompression. Additional isobaric heating at 1.07 GPa was performed in the mid-IR regime, which clearly revealed an onset of decomposition at 360 °C. Further x-ray or neutron diffraction, which are needed to fully resolve the cause of observed changes above 2 and 5 GPa, are ongoing.
High pressure infrared (IR) measurements of the insensitive explosive, 1,1-diamino-2,2-dinitroethylene (DADNE or FOX-7), have been performed in the far- and mid-IR spectral regions up to ∼28 GPa using a synchrotron source. Petroleum jelly and KBr were employed as the pressurizing media for the far- and mid-IR experiments, respectively. In both experiments, IR spectra were collected at various pressures both in compression and decompression to determine reversibility under pressure cycling. There is evidence for at least two and possibly three phase transitions in the samples at pressures near 2, 5, and10 GPa, respectively. In the high frequency region (∼3000–3300 cm−1), the NH2 symmetric and antisymmetric vibrational modes soften with increasing pressure, suggesting strengthening intermolecular hydrogen bonding, and then stiffen with further pressure increase. At higher pressures (above 5 GPa), we suspect progressive flattening of the zig zag structure characteristic of the α phase occurs, which was observed in the low temperature, quenched γ phase. FOX-7 was also observed to survive pressure cycling up to 28 GPa contrary to earlier reports of pressure-induced molecular decomposition.
The pressure-temperature (P-T) phase diagram of ammonium nitrate (AN) [NH(4)NO(3)] has been determined using synchrotron x-ray diffraction (XRD) and Raman spectroscopy measurements. Phase boundaries were established by characterizing phase transitions to the high temperature polymorphs during multiple P-T measurements using both XRD and Raman spectroscopy measurements. At room temperature, the ambient pressure orthorhombic (Pmmn) AN-IV phase was stable up to 45 GPa and no phase transitions were observed. AN-IV phase was also observed to be stable in a large P-T phase space. The phase boundaries are steep with a small phase stability regime for high temperature phases. A P-V-T equation of state based on a high temperature Birch-Murnaghan formalism was obtained by simultaneously fitting the P-V isotherms at 298, 325, 446, and 467 K, thermal expansion data at 1 bar, and volumes from P-T ramping experiments. Anomalous thermal expansion behavior of AN was observed at high pressure with a modest negative thermal expansion in the 3-11 GPa range for temperatures up to 467 K. The role of vibrational anharmonicity in this anomalous thermal expansion behavior has been established using high P-T Raman spectroscopy.
Diamond anvil cells (DAC) coupled with x-ray diffraction (XRD) measurements are one of the primary techniques for investigating structural stability of materials at high pressure-temperature (P-T) conditions. DAC-XRD has been predominantly used to resolve structural information at set P-T conditions and, consequently, provides P-T phase diagram information on a broad range of materials. With advances in large scale synchrotron x-ray facilities and corresponding x-ray diagnostic capabilities, it is now becoming possible to perform sub-second time resolved measurements on micron sized DAC samples. As a result, there is an opportunity to gain valuable information about the kinetics of structural phase transformations and extend our understanding of material behavior at high P-T conditions. Using DAC-XRD time resolved measurements, we have investigated the kinetics of the α to ω transformation in zirconium. We observe a clear time and pressure dependence in the martensitic α-ω transition as a function of pressure-jump, i.e., drive pressure. The resulting data are fit using available kinetics models, which can provide further insight into transformation mechanism that influence transformation kinetics. Our results help shed light on the discrepancies observed in previous measurements of the α-ω transition pressure in zirconium.
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