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Title: High pressure-high temperature phase diagram of an energetic crystal: Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)

Abstract

Raman spectroscopy was used to examine the high pressure-high temperature structural and chemical stability of an insensitive, high-performance energetic crystal – dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50). The phase diagram was determined over 8 GPa and (293-760) K. Under isobaric heating, the melting/decomposition of TKX-50 is preceded by a transformation to two consecutive high-temperature intermediates; a lower-temperature intermediate – diammonium 5,5’-bistetrazole-1,1'-diolate, and a higher-temperature intermediate – dihydroxylammonium 5,5'-bistetrazolate and/or diammonium 5,5'-bistetrazolate. Pressure strongly increases the transition temperatures for these transformations and subsequent decomposition. As a result, significant increase in the chemical stability of TKX-50 and intermediates with pressure was attributed to a suppression of hydrogen-transfer.

Authors:
 [1]; ORCiD logo [2];  [1]
  1. Washington State Univ., Pullman, WA (United States)
  2. Washington State Univ., Pullman, WA (United States); U.S. Naval Research Lab., Washington, D.C. (United States)
Publication Date:
Research Org.:
Washington State Univ., Pullman, WA (United States). Inst. for Shock Physics
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP) (NA-10)
OSTI Identifier:
1363636
Alternate Identifier(s):
OSTI ID: 1415302
Grant/Contract Number:
NA0002007
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Physics Letters
Additional Journal Information:
Journal Volume: 679; Journal Issue: C; Journal ID: ISSN 0009-2614
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; high pressure; high temperature; high explosive; phase diagram; Raman spectroscopy; TKX-50

Citation Formats

Dreger, Z. A., Breshike, C. J., and Gupta, Y. M. High pressure-high temperature phase diagram of an energetic crystal: Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50). United States: N. p., 2017. Web. doi:10.1016/j.cplett.2017.05.019.
Dreger, Z. A., Breshike, C. J., & Gupta, Y. M. High pressure-high temperature phase diagram of an energetic crystal: Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50). United States. doi:10.1016/j.cplett.2017.05.019.
Dreger, Z. A., Breshike, C. J., and Gupta, Y. M. Mon . "High pressure-high temperature phase diagram of an energetic crystal: Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)". United States. doi:10.1016/j.cplett.2017.05.019. https://www.osti.gov/servlets/purl/1363636.
@article{osti_1363636,
title = {High pressure-high temperature phase diagram of an energetic crystal: Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)},
author = {Dreger, Z. A. and Breshike, C. J. and Gupta, Y. M.},
abstractNote = {Raman spectroscopy was used to examine the high pressure-high temperature structural and chemical stability of an insensitive, high-performance energetic crystal – dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50). The phase diagram was determined over 8 GPa and (293-760) K. Under isobaric heating, the melting/decomposition of TKX-50 is preceded by a transformation to two consecutive high-temperature intermediates; a lower-temperature intermediate – diammonium 5,5’-bistetrazole-1,1'-diolate, and a higher-temperature intermediate – dihydroxylammonium 5,5'-bistetrazolate and/or diammonium 5,5'-bistetrazolate. Pressure strongly increases the transition temperatures for these transformations and subsequent decomposition. As a result, significant increase in the chemical stability of TKX-50 and intermediates with pressure was attributed to a suppression of hydrogen-transfer.},
doi = {10.1016/j.cplett.2017.05.019},
journal = {Chemical Physics Letters},
number = C,
volume = 679,
place = {United States},
year = {Mon May 08 00:00:00 EDT 2017},
month = {Mon May 08 00:00:00 EDT 2017}
}

Journal Article:
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  • The structural response of a novel, insensitive energetic crystal—dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)—was examined under high pressure. Using synchrotron single-crystal X-ray diffraction measurements, details of molecular, intermolecular, and crystal changes were determined to ~10 GPa to understand its structural stability. The experimental results showed that TKX-50 exhibits highly anisotropic compression and significantly lower volume compressibility than currently known energetic crystals. These results are found to be in general agreement with our previous predictions from the DFT calculations. Additionally, the experimental data revealed anomalous compression—an expansion of the unit cell along the a axis (negative linear compressibility, NLC) upon compression to ~3 GPa.more » The structural analyses demonstrated that this unusual effect, the first such observation in an energetic crystal, is a consequence of the highly anisotropic response of 3D motifs, comprised of two parallel anions [(C 2N 8O 2) 2–] linked with two cations [(NH 3OH) +] through four strong hydrogen bonds. The present results demonstrate that the structural stability of TKX-50 is controlled by the strong and highly anisotropic intermolecular interactions, and these may contribute to its shock insensitivity.« less
  • The structural response of a novel, insensitive energetic crystal—dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)—was examined under high pressure. Using synchrotron single-crystal X-ray diffraction measurements, details of molecular, intermolecular, and crystal changes were determined to ~10 GPa to understand its structural stability. The experimental results showed that TKX-50 exhibits highly anisotropic compression and significantly lower volume compressibility than currently known energetic crystals. These results are found to be in general agreement with our previous predictions from the DFT calculations. Additionally, the experimental data revealed anomalous compression—an expansion of the unit cell along the a axis (negative linear compressibility, NLC) upon compression to ~3 GPa.more » The structural analyses demonstrated that this unusual effect, the first such observation in an energetic crystal, is a consequence of the highly anisotropic response of 3D motifs, comprised of two parallel anions [(C 2N 8O 2) 2–] linked with two cations [(NH 3OH) +] through four strong hydrogen bonds. Finally, the present results demonstrate that the structural stability of TKX-50 is controlled by the strong and highly anisotropic intermolecular interactions, and these may contribute to its shock insensitivity.« less
  • In this study, 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 boundarymore » (~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.« less