High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene

Bishop, M. M.; Chellappa, R. S.; Liu, Z.; Preston, D. N.; Sandstrom, M. M.; Dattelbaum, D. M.; Vohra, Y. K.; Velisavljevic, N.

doi:10.1088/1742-6596/500/5/052005

Title: High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene

Full Record
Other Related Research

Abstract

Here, 1,1-diamino-2,2-dinitroethylene (FOX-7) is a low sensitivity energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ). In this study, we have investigated the high pressure-temperature stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra and corresponding differential scanning calorimetry (DSC) measurements confirmed the known α → β (~110 °C) and β → γ (~160 °C) structural phase transitions; as well as, indicated an additional transition γ → δ (~210 °C), with the δ phase being stable up to ~251 degree C prior to decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa, revealed a potential α → β transition that could occur as early as 180 degree C, while β → β+δ phase transition shifted to ~300 °C with suppression of γ phase. Decomposition was observed slightly above 325 °C at 0.9 GPa..

Authors:

Bishop, M. M. ^[1]; Chellappa, R. S. ^[2]; Liu, Z. ^[3]; Preston, D. N. ^[2]; Sandstrom, M. M. ^[2]; Dattelbaum, D. M. ^[2]; Vohra, Y. K. ^[4]; Velisavljevic, N. ^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Alabama at Birmingham, Birmingham, AL (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Carnegie Institution of Washington, Washington, D.C. (United States)
Univ. of Alabama at Birmingham, Birmingham, AL (United States)

Publication Date:: Wed May 07 00:00:00 EDT 2014

Research Org.:: Univ. of Alabama, Birmingham, AL (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1251169

Grant/Contract Number:: NA0002014

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physics. Conference Series (Online)

Additional Journal Information:: Journal Name: Journal of Physics. Conference Series (Online); Journal Volume: 500; Journal Issue: 5; Journal ID: ISSN 1742-6596

Publisher:: Institute of Physics (IOP)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; energetic materials; phase diagrams; high pressure

Citation Formats


                    Bishop, M. M., Chellappa, R. S., Liu, Z., Preston, D. N., Sandstrom, M. M., Dattelbaum, D. M., Vohra, Y. K., and Velisavljevic, N. High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene.  United States: N. p., 2014. 
Web.  doi:10.1088/1742-6596/500/5/052005.

Copy to clipboard


                    Bishop, M. M., Chellappa, R. S., Liu, Z., Preston, D. N., Sandstrom, M. M., Dattelbaum, D. M., Vohra, Y. K., & Velisavljevic, N. High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene.  United States.  https://doi.org/10.1088/1742-6596/500/5/052005

Copy to clipboard


                    Bishop, M. M., Chellappa, R. S., Liu, Z., Preston, D. N., Sandstrom, M. M., Dattelbaum, D. M., Vohra, Y. K., and Velisavljevic, N. Wed .  
"High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene".  United States.  https://doi.org/10.1088/1742-6596/500/5/052005.  https://www.osti.gov/servlets/purl/1251169.

Copy to clipboard


                    
@article{osti_1251169,

  title        = {High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene},

  author       = {Bishop, M. M. and Chellappa, R. S. and Liu, Z. and Preston, D. N. and Sandstrom, M. M. and Dattelbaum, D. M. and Vohra, Y. K. and Velisavljevic, N.},

  abstractNote = {Here, 1,1-diamino-2,2-dinitroethylene (FOX-7) is a low sensitivity energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ). In this study, we have investigated the high pressure-temperature stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra and corresponding differential scanning calorimetry (DSC) measurements confirmed the known α → β (~110 °C) and β → γ (~160 °C) structural phase transitions; as well as, indicated an additional transition γ → δ (~210 °C), with the δ phase being stable up to ~251 degree C prior to decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa, revealed a potential α → β transition that could occur as early as 180 degree C, while β → β+δ phase transition shifted to ~300 °C with suppression of γ phase. Decomposition was observed slightly above 325 °C at 0.9 GPa..},

  doi          = {10.1088/1742-6596/500/5/052005},

  journal      = {Journal of Physics. Conference Series (Online)},

  number       = 5,

  volume       = 500,

  place        = {United States},

  year         = {Wed May 07 00:00:00 EDT 2014},

  month        = {Wed May 07 00:00:00 EDT 2014}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1088/1742-6596/500/5/052005

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 8 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

High pressure–temperature phase diagram of 1,1-diamino-2,2-dinitroethylene (FOX-7)

Journal Article Bishop, Matthew M. ; Velisavljevic, Nenad ; Chellappa, Raja ; ... - Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

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) withmore »« less
Cited by 22
https://doi.org/10.1021/acs.jpca.5b07811

Full Text Available
Phase diagram and decomposition of 1,1-diamino-2,2-dinitroethene single crystals at high pressures and temperatures

Journal Article Dreger, Zbigniew A. ; Tao, Yuchuan ; Gupta, Yogendra M. - Journal of Physical Chemistry. C

The high pressure-high temperature (HP-HT) phase diagram and decomposition of FOX-7, central to understanding its stability and reactivity, were determined using optical spectroscopy and imaging measurements in hydrostatically compressed and heated single crystals. Boundaries between various FOX-7 phases (α, α’, β, γ, and ε) and melting/decomposition curves were established up to 10 GPa and 750 K. Main findings are: (i) a triple point is observed between α, β, and γ phases ~ 0.6 GPa and ~ 535 K, (ii) previously suggested δ phase is not a new phase but is partly decomposed γ phase, (iii) the α-α’ transition takes placemore »« less
Cited by 14
https://doi.org/10.1021/acs.jpcc.6b02360

Full Text Available
Effect of charged and excited states on the decomposition of 1,1-diamino-2,2-dinitroethylene molecules

Journal Article Kimmel, Anna V ; Sushko, Peter V ; Shluger, Alexander L ; ... - Journal of Chemical Physics

The authors have calculated the electronic structure of individual 1,1-diamino-2,2-dinitroethylene molecules (FOX-7) in the gas phase by means of density functional theory with the hybrid B3LYP functional and 6-31+G(d,p) basis set and considered their dissociation pathways. Positively and negatively charged states as well as the lowest excited states of the molecule were simulated. They found that charging and excitation can not only reduce the activation barriers for decomposition reactions but also change the dominating chemistry from endo- to exothermic type. In particular, they found that there are two competing primary initiation mechanisms of FOX-7 decomposition: C-NO{sub 2} bond fission andmore »« less
https://doi.org/10.1063/1.2741530
High-pressure crystal structures of an insensitive energetic crystal: 1,1-diamino-2,2-dinitroethene

Journal Article Dreger, Zbigniew A. ; Stash, Adam I. ; Yu, Zhi -Gang ; ... - Journal of Physical Chemistry. C

Understanding the insensitivity/stability of insensitive high explosive crystals requires detailed structural information at high pressures and high temperatures of interest. Synchrotron single crystal x-ray diffraction experiments were used to determine the high-pressure structures of 1,1-diamino-2,2-dinitroethene (FOX-7), a prototypical insensitive high explosive. The phase transition around 4.5 GPa was investigated and the structures were determined at 4.27 GPa (α’-phase) and 5.9 GPa (ε-phase). The α’-phase (monoclinic, P2₁/n), structurally indistinguishable from the ambient α-phase, transforms to the new ε-phase (triclinic, P1). The most notable features of the ε-phase, compared to the α’-phase, are: formation of planar layers and flattening of molecules. Densitymore »« less
Cited by 33
https://doi.org/10.1021/acs.jpcc.5b10644

Full Text Available
High-Pressure Structural Response of an Insensitive Energetic Crystal: 1,1-Diamino-2,2-dinitroethene (FOX-7)

Journal Article Dreger, Zbigniew A. ; Stash, Adam I. ; Yu, Zhi-Gang ; ... - Journal of Physical Chemistry. C

Here, high-pressure structural response of an insensitive energetic crystal—1,1-diamino-2,2-dinitroethene (FOX-7)—was examined to gain insight into its structural and chemical stability and to obtain isothermal compression data. Using synchrotron single-crystal X-ray diffraction measurements, details of pressure-induced structural changes to 12.8 GPa were determined across three FOX-7 phases: α (P2₁/n), α' (P2₁/n), and ε (P1). We found that the C–NO₂ bond is the most compressible chemical bond, and high pressure significantly reduces and homogenizes the length of H bonds in the hydrogen-bond network. The α'-ε phase transition, at 4.5 GPa, significantly affects all molecular and crystal properties, whereas the α–α' transition, atmore »« less
Cited by 17
https://doi.org/10.1021/acs.jpcc.6b10010

Full Text Available

Similar Records