Skip to main content

Advertisement

SpringerLink
Log in

A Kinetics Investigation on the Nitro-Nitrite Rearrangement Mediated Thermal Decomposition of High Temperature Monoclinic Phase of 1,1-Diamino-2,2-Dinitroethylene (γ-Fox-7)

  • Regular Article
  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

1,1-Diamino-2,2-dinitroethylene (DADNE), commonly known as FOX-7, is one of the novel high energy density molecules recently developed along with CL-20, TNAZ and ADN. DADNE is well-known for its insensitive nature and this has motivated the research in understanding the thermal and explosive decomposition behaviour of DADNE. We have studied the thermal decomposition kinetics of DADNE employing two isoconversional methods viz., Friedman’s differential method and Vyazovkin’s non-linear integral method. For the study, Differential Scanning Calorimetry as well as Thermogravimetry data collected at lower heating rates (<5°C/min) were used. This study indicated a four stage decomposition behaviour of DADNE, where each stage is characterised by different activation energy. Computed activation energy values have been used to understand the thermal decomposition mechanism of DADNE.

Experimental investigations of thermal decomposition kinetics of 1,1-Diamino-2,2-Dinitroethylene (γ-Fox-7), DADNE at a lower heating rate was studied using Differential Scanning Calorimetry and Thermogravimetry. The results suggest that DADNE exhibits two different decomposition pathways. During thermogravimetric analysis it undergoes nitronitrite rearrangement-mediated decomposition leading to the formation of CO, H2O and N2.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Scheme 2
Scheme 3
Scheme 4
Scheme 5
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9

Similar content being viewed by others

References

  1. Latypov N V, Bergman J, Langlet A, Wellmar U and Bemm U 1998 Synthesis and reactions of 1,1-diamino-2,2-dinitroethylene Tetrahedron 54 11525

    Article  CAS  Google Scholar 

  2. Jalovy Z, Ek S, Ottis J, Dudek K, Ruzicka A, Lycka A and Latypov L V 2013 Scalable synthesis of 1,1-Diamino-2,2-dinitroethene without hazardous intermediates or by-Products J. Energy Mater. 31 87

    Article  CAS  Google Scholar 

  3. Lochert I J 2001 FOX-7: A new insensitive explosive Technical Report DSTO-TR-1238 PR

  4. Mandal A K, Thanigaivelan U, Pandey R K, Asthana S, Khomane R B and Kulkarni B D 2012 Preparation of Spherical Particles of 1,1-Diamino-2,2-dinitroethene (FOX-7) Using a Micellar Nanoreactor Org. Process Res. Dev. 16 1711

    Article  CAS  Google Scholar 

  5. Gindulyte A, Massa L, Huang L and Karle J 1999 Proposed mechanism of 1,1-diamino-dinitroethylene decomposition: A density functional theory study J. Phys. Chem. 103 11045

    Article  CAS  Google Scholar 

  6. Kimmel A V, Sushko P V, Shluger A L and Kuklja M M 2007 Effect of charged and excited states on the decomposition of 1,1-diamino-2,2-dinitroethylene molecules J. Chem. Phys. 126 234711

    Article  Google Scholar 

  7. Zheng Z, Xu J and Zhao J 2010 First-principles studies on the thermal decomposition behaviour of FOX-7 High Pressure Res. 30 301

    Article  CAS  Google Scholar 

  8. Yuan B, Yu Z and Bernstein E R 2014 Initial decomposition mechanism for the energy release from electronically excited energetic materials: FOX-7 (1,1-diamino-2,2-dinitroethene, C2H4N4O4) J. Chem. Phys. 140 074708

    Article  Google Scholar 

  9. Kiselev V G and Gritsan N P 2014 Unexpected Primary Reactions for Thermolysis of 1,1-Diamino-2,2-dinitroethylene (FOX-7) Revealed by ab Initio Calculations J. Phys. Chem. 118 8002

    Article  CAS  Google Scholar 

  10. Liu Y, Li F and Sun H 2014 Thermal decomposition of FOX7 studied by ab initio molecular dynamics simulations Theor. Chem. Acc. 133 1567

    Article  Google Scholar 

  11. Booth R S and Butler L J 2014 Thermal decomposition pathways for 1,1-diamino-2,2-dinitroethene (FOX-7) J. Chem. Phys. 141 134315

    Article  Google Scholar 

  12. De Klerk W P C, Popescu C and van der Heijden A E D M 2003 Study on the decomposition kinetics of FOX-7 and HNF J. Therm. Anal. Cal. 72 955

  13. Sinditskii V P, Levshenkov A I, Egorshev V Y and Serushkin V V 2003 Study on combustion and thermal decomposition of 1,1-Diamino-2,2-dinitroethylene (FOX-7) 30 th International pyrotechnics seminar, France

  14. Ostmark H, Bergman H, Bemm U, Goede P, Holmgren E, Johansson M, Langlet A, Latypov N V, Pettersson M–L, Wingborg N, Vorde C, Stenmark H, Karlsson L and Hihkio M 2001 2,2-dinitro-ethene-1,1-diamine (FOX-7) - properties, analysis and scale-up, 32 nd International Annual Conference of ICT on Energetic Materials - Ignition, Combustion and Detonation, Germany

  15. Wang J, He S, Li Z, Jing X, Zhang M and Jiang Z 2009 Synthesis of chrysalis-like CuO nanocrystals and their catalytic activity in the thermal decomposition of ammonium perchlorate J. Chem. Sci. 121 1077

    Article  CAS  Google Scholar 

  16. Zhao G, Jia J and Wu H 2016 Design and selection of triazole-based compounds with high energetic properties and stabilities J. Chem. Sci. 128 1223

    Article  CAS  Google Scholar 

  17. Vyazovkin S, Burnham A K, Criado J M, Perez-Maqueda L A, Popescu C and Sbirrazzuoli N 2011 ICATC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data Thermochim. Acta 520 1

    Article  CAS  Google Scholar 

  18. Vargeese A A 2015 Pressure effects on thermal decomposition reactions: A thermo-kinetic investigation RSC Adv. 5 78598

    Article  CAS  Google Scholar 

  19. Vargeese A A 2016 A kinetic investigation on the mechanism and activity of copper oxide nanorods on the thermal decomposition of propellants Combust. Flame 165 354

    Article  CAS  Google Scholar 

  20. Vargeese A A and Muralidharan K 2012 Kinetics and mechanism of hydrothermally prepared copper oxide nanorodcatalyzed decomposition of ammonium nitrate Appl. Catal. A 447–448 171

    Article  Google Scholar 

  21. Flynn J H and Wall L A 1966 General treatment of the thermogravimetry of polymers J. Res. Natl. Bur. Stan. A Phys. Chem. 70 487

    Article  CAS  Google Scholar 

  22. Ozawa T 1965 A new method analysing thermogravimetric data Bull. Chem. Soc. Jpn. 38 1881

    Article  CAS  Google Scholar 

  23. Friedman H L 1965 Kinetics of thermal degradation of char-forming plastics from thermogravimetryApplication to a phenolic plastic J. Polym. Sci. C 50 183

    Google Scholar 

  24. Vyazovkin S and Dollimore D 1996 Linear and nonlinear procedures in isoconversional computations of the activation energy of nonisothermal reactions in solids J. Chem. Inf. Comput. Sci. 36 42

    Article  CAS  Google Scholar 

  25. Senum G I and Yang R T 1977 Rational approximations of the integral of the Arrhenius function J. Thermal. Anal. 11 445

    Article  Google Scholar 

  26. Bellamy A J 2007 In High Energy Density Materials T M Klapotke (Ed.) (Heidelberg: Springer-Verlag) p. 1

  27. Crawford M J, Evers J, Gobel M, Klapotke T M, Mayer P, Oehlinger G and Welch J M 2007 AAA γ-FOX-7: Structure of a high energy density material immediately prior to decomposition Propellants Explos. Pyrotech. 32 478

    Article  CAS  Google Scholar 

  28. Bernstein J 2002 In Polymorphism in Molecular Crystals (New York: Oxford University Press) p. 223

  29. Pettersson A, Goede P, Kjellstrom A and Wallin S 2004 Mass spectrometric study on FOX-7 decomposition Technical Report FOI-R-1319

  30. Boldyrev V V 2006 Thermal decomposition of ammonium perchlorate Thermochim. Acta 443 16

    Article  Google Scholar 

Download references

Acknowledgements

The authors thank Dr. Mija S. J. (NIT Calicut) for MATLAB code (for kinetic computations). This research was funded by Defence Research and Development Organization (India) in the form of grant-in-aid to Advanced Centre of Research in High Energy Materials (ACRHEM).

Author information

Authors and Affiliations

  1. Advanced Centre of Research in High Energy Materials (ACRHEM), University of Hyderabad, Hyderabad, 500 046, India

    KRANTHI CHATRAGADDA & ANUJ A VARGEESE

Authors
  1. KRANTHI CHATRAGADDA
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. ANUJ A VARGEESE
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to ANUJ A VARGEESE.

Additional information

Supplementary Information (SI)

The theoretical background of kinetic analysis, thermal cycling data of DADNE, phase transition data by TGA, DSC traces of DADNE decomposition and activation energy calculated by nonlinear integral isoconversional method are given as Supplementary Information. Supplementary Information is available at www.ias.ac.in/chemsci.

Electronic supplementary material

Below is the link to the electronic supplementary material.

(DOCX 633 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

CHATRAGADDA, K., VARGEESE, A.A. A Kinetics Investigation on the Nitro-Nitrite Rearrangement Mediated Thermal Decomposition of High Temperature Monoclinic Phase of 1,1-Diamino-2,2-Dinitroethylene (γ-Fox-7). J Chem Sci 129, 281–288 (2017). https://doi.org/10.1007/s12039-016-1220-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12039-016-1220-z

Keywords

Search

Navigation