Research output: Contribution to journal › Article › peer-review
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. et al.
In: Physical Chemistry Chemical Physics, Vol. 19, No. 1, 21.12.2016, p. 436-449.Research output: Contribution to journal › Article › peer-review
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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 - 2016/12/21
Y1 - 2016/12/21
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).
KW - NITROGEN-RICH SALTS
KW - N-OXIDE
KW - 5-AMINOTETRAZOLE
KW - CHEMISTRY
KW - AMINOTETRAZOLES
KW - DECONVOLUTION
KW - PROPELLANTS
KW - PERFORMANCE
KW - DERIVATIVES
KW - EXPLOSIVES
UR - http://www.scopus.com/inward/record.url?scp=85016162922&partnerID=8YFLogxK
U2 - 10.1039/c6cp06498a
DO - 10.1039/c6cp06498a
M3 - Article
C2 - 27905609
AN - SCOPUS:85016162922
VL - 19
SP - 436
EP - 449
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 1
ER -
ID: 8673246