Pursuing reliable thermal analysis techniques for energetic materials

Decomposition kinetics and thermal stability of dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50)

Nikita V. Muravyev, Konstantin A. Monogarov, Andrey F. Asachenko, Mikhail S. Nechaev, Ivan V. Ananyev, Igor V. Fomenkov, Vitaly G. Kiselev, Alla N. Pivkina

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Thermal decomposition of a novel promising high-performance explosive dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) was studied using a number of thermal analysis techniques (thermogravimetry, differential scanning calorimetry, and accelerating rate calorimetry, ARC). To obtain more comprehensive insight into the kinetics and mechanism of TKX-50 decomposition, a variety of complementary thermoanalytical experiments were performed under various conditions. Non-isothermal and isothermal kinetics were obtained at both atmospheric and low (up to 0.3 Torr) pressures. The gas products of thermolysis were detected in situ using IR spectroscopy, and the structure of solid-state decomposition products was determined by X-ray diffraction and scanning electron microscopy. Diammonium 5,5′-bistetrazole-1,1′-diolate (ABTOX) was directly identified to be the most important intermediate of the decomposition process. The important role of bistetrazole diol (BTO) in the mechanism of TKX-50 decomposition was also rationalized by thermolysis experiments with mixtures of TKX-50 and BTO. Several widely used thermoanalytical data processing techniques (Kissinger, isoconversional, formal kinetic approaches, etc.) were independently benchmarked against the ARC data, which are more germane to the real storage and application conditions of energetic materials. Our study revealed that none of the Arrhenius parameters reported before can properly describe the complex two-stage decomposition process of TKX-50. In contrast, we showed the superior performance of the isoconversional methods combined with isothermal measurements, which yielded the most reliable kinetic parameters of TKX-50 thermolysis. In contrast with the existing reports, the thermal stability of TKX-50 was determined in the ARC experiments to be lower than that of hexogen, but close to that of hexanitrohexaazaisowurtzitane (CL-20).

Original languageEnglish
Pages (from-to)436-449
Number of pages14
JournalPhysical Chemistry Chemical Physics
Volume19
Issue number1
DOIs
Publication statusPublished - 2017
Externally publishedYes

Fingerprint

Thermoanalysis
thermal analysis
Thermodynamic stability
thermal stability
Thermolysis
Decomposition
decomposition
Kinetics
kinetics
heat measurement
Experiments
Calorimetry
products
thermogravimetry
Kinetic parameters
thermal decomposition
Thermogravimetric analysis
Differential scanning calorimetry
Infrared spectroscopy
Pyrolysis

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Pursuing reliable thermal analysis techniques for energetic materials : Decomposition kinetics and thermal stability of dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50). / Muravyev, Nikita V.; Monogarov, Konstantin A.; Asachenko, Andrey F.; Nechaev, Mikhail S.; Ananyev, Ivan V.; Fomenkov, Igor V.; Kiselev, Vitaly G.; Pivkina, Alla N.

In: Physical Chemistry Chemical Physics, Vol. 19, No. 1, 2017, p. 436-449.

Research output: Contribution to journalArticle

Muravyev, Nikita V. ; Monogarov, Konstantin A. ; Asachenko, Andrey F. ; Nechaev, Mikhail S. ; Ananyev, Ivan V. ; Fomenkov, Igor V. ; Kiselev, Vitaly G. ; Pivkina, Alla N. / Pursuing reliable thermal analysis techniques for energetic materials : Decomposition kinetics and thermal stability of dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50). In: Physical Chemistry Chemical Physics. 2017 ; Vol. 19, No. 1. pp. 436-449.
@article{51050fa7da45468a9516777c5617359c,
title = "Pursuing reliable thermal analysis techniques for energetic materials: Decomposition kinetics and thermal stability of dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50)",
abstract = "Thermal decomposition of a novel promising high-performance explosive dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) was studied using a number of thermal analysis techniques (thermogravimetry, differential scanning calorimetry, and accelerating rate calorimetry, ARC). To obtain more comprehensive insight into the kinetics and mechanism of TKX-50 decomposition, a variety of complementary thermoanalytical experiments were performed under various conditions. Non-isothermal and isothermal kinetics were obtained at both atmospheric and low (up to 0.3 Torr) pressures. The gas products of thermolysis were detected in situ using IR spectroscopy, and the structure of solid-state decomposition products was determined by X-ray diffraction and scanning electron microscopy. Diammonium 5,5′-bistetrazole-1,1′-diolate (ABTOX) was directly identified to be the most important intermediate of the decomposition process. The important role of bistetrazole diol (BTO) in the mechanism of TKX-50 decomposition was also rationalized by thermolysis experiments with mixtures of TKX-50 and BTO. Several widely used thermoanalytical data processing techniques (Kissinger, isoconversional, formal kinetic approaches, etc.) were independently benchmarked against the ARC data, which are more germane to the real storage and application conditions of energetic materials. Our study revealed that none of the Arrhenius parameters reported before can properly describe the complex two-stage decomposition process of TKX-50. In contrast, we showed the superior performance of the isoconversional methods combined with isothermal measurements, which yielded the most reliable kinetic parameters of TKX-50 thermolysis. In contrast with the existing reports, the thermal stability of TKX-50 was determined in the ARC experiments to be lower than that of hexogen, but close to that of hexanitrohexaazaisowurtzitane (CL-20).",
author = "Muravyev, {Nikita V.} and Monogarov, {Konstantin A.} and Asachenko, {Andrey F.} and Nechaev, {Mikhail S.} and Ananyev, {Ivan V.} and Fomenkov, {Igor V.} and Kiselev, {Vitaly G.} and Pivkina, {Alla N.}",
year = "2017",
doi = "10.1039/c6cp06498a",
language = "English",
volume = "19",
pages = "436--449",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "1",

}

TY - JOUR

T1 - Pursuing reliable thermal analysis techniques for energetic materials

T2 - Decomposition kinetics and thermal stability of dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50)

AU - Muravyev, Nikita V.

AU - Monogarov, Konstantin A.

AU - Asachenko, Andrey F.

AU - Nechaev, Mikhail S.

AU - Ananyev, Ivan V.

AU - Fomenkov, Igor V.

AU - Kiselev, Vitaly G.

AU - Pivkina, Alla N.

PY - 2017

Y1 - 2017

N2 - Thermal decomposition of a novel promising high-performance explosive dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) was studied using a number of thermal analysis techniques (thermogravimetry, differential scanning calorimetry, and accelerating rate calorimetry, ARC). To obtain more comprehensive insight into the kinetics and mechanism of TKX-50 decomposition, a variety of complementary thermoanalytical experiments were performed under various conditions. Non-isothermal and isothermal kinetics were obtained at both atmospheric and low (up to 0.3 Torr) pressures. The gas products of thermolysis were detected in situ using IR spectroscopy, and the structure of solid-state decomposition products was determined by X-ray diffraction and scanning electron microscopy. Diammonium 5,5′-bistetrazole-1,1′-diolate (ABTOX) was directly identified to be the most important intermediate of the decomposition process. The important role of bistetrazole diol (BTO) in the mechanism of TKX-50 decomposition was also rationalized by thermolysis experiments with mixtures of TKX-50 and BTO. Several widely used thermoanalytical data processing techniques (Kissinger, isoconversional, formal kinetic approaches, etc.) were independently benchmarked against the ARC data, which are more germane to the real storage and application conditions of energetic materials. Our study revealed that none of the Arrhenius parameters reported before can properly describe the complex two-stage decomposition process of TKX-50. In contrast, we showed the superior performance of the isoconversional methods combined with isothermal measurements, which yielded the most reliable kinetic parameters of TKX-50 thermolysis. In contrast with the existing reports, the thermal stability of TKX-50 was determined in the ARC experiments to be lower than that of hexogen, but close to that of hexanitrohexaazaisowurtzitane (CL-20).

AB - Thermal decomposition of a novel promising high-performance explosive dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) was studied using a number of thermal analysis techniques (thermogravimetry, differential scanning calorimetry, and accelerating rate calorimetry, ARC). To obtain more comprehensive insight into the kinetics and mechanism of TKX-50 decomposition, a variety of complementary thermoanalytical experiments were performed under various conditions. Non-isothermal and isothermal kinetics were obtained at both atmospheric and low (up to 0.3 Torr) pressures. The gas products of thermolysis were detected in situ using IR spectroscopy, and the structure of solid-state decomposition products was determined by X-ray diffraction and scanning electron microscopy. Diammonium 5,5′-bistetrazole-1,1′-diolate (ABTOX) was directly identified to be the most important intermediate of the decomposition process. The important role of bistetrazole diol (BTO) in the mechanism of TKX-50 decomposition was also rationalized by thermolysis experiments with mixtures of TKX-50 and BTO. Several widely used thermoanalytical data processing techniques (Kissinger, isoconversional, formal kinetic approaches, etc.) were independently benchmarked against the ARC data, which are more germane to the real storage and application conditions of energetic materials. Our study revealed that none of the Arrhenius parameters reported before can properly describe the complex two-stage decomposition process of TKX-50. In contrast, we showed the superior performance of the isoconversional methods combined with isothermal measurements, which yielded the most reliable kinetic parameters of TKX-50 thermolysis. In contrast with the existing reports, the thermal stability of TKX-50 was determined in the ARC experiments to be lower than that of hexogen, but close to that of hexanitrohexaazaisowurtzitane (CL-20).

UR - http://www.scopus.com/inward/record.url?scp=85016162922&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85016162922&partnerID=8YFLogxK

U2 - 10.1039/c6cp06498a

DO - 10.1039/c6cp06498a

M3 - Article

VL - 19

SP - 436

EP - 449

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 1

ER -