TY - JOUR

T1 - Too fast and too furious: thermoanalytical and quantum chemical study of the thermal stability of 4,4′-dinitro-3,3′-diazenofuroxan

AU - Kiselev, Vitaly G.

AU - Sadykov, Artem R.

AU - Melnikov, Igor N.

AU - Fomenkov, Igor V.

AU - Fershtat, Leonid L.

AU - Pivkina, Alla N.

AU - Muravyev, Nikita V.

N1 - The authors acknowledge the support of this work by the Russian Science Foundation (Project 19-73-20217-P). The authors are thankful to Dr Dmitry M. Bystrov (Zelinsky Institute of Organic Chemistry) for technical assistance. The support by the Supercomputer Center of Novosibirsk State University and Irkutsk Supercomputer Center SB RAS through the use of their computational facilities is also acknowledged.

PY - 2024/12/4

Y1 - 2024/12/4

N2 - Novel energetic materials (EM) often combine two intrinsically counter trends, viz., a high energy density and mediocre safety parameters, like thermal stability and sensitivity toward mechanical stimuli. A rational design of promising EMs requires a proper understanding of their thermal stability at both macroscopic and molecular levels. In the present contribution, we studied in detail the thermal stability of 4,4′-dinitro-3,3′-diazenofuroxan (DDF), an ultrahigh-performance energetic material with a reliable experimental detonation velocity being very close to 10 km s−1. To this end, we employed a set of complementary thermoanalytical (DSC and TGA in the solid state along with advanced thermokinetic models, optical microscopy, and gas products detection) and theoretical techniques (DLPNO-CCSD(T) quantum chemical calculations). According to the DSC measurements, the solid-state thermolysis of DDF turned out to be a complex three-step process. The decomposition commences at ∼85 °C and the most intense heat release occurs at ∼130 °C depending on the heating rate. In order to properly describe the kinetics of DDF thermolysis beyond the simple Kissinger and Friedman methods, we applied a “top-down” kinetic approach resulting in the formal model comprised of three independent stages. A flexible Kolmogorov-Johnson-Mehl-Avrami-Erofeev equation was applied for the first decomposition stage along with the extended Prout-Tompkins equation for the second and third processes, respectively. The formal exponent in the former equation turned out to be close to a second order, thus suggesting a two-dimensional nuclei-growth model for the first stage. We rationalized this fact with the aid of optical microscopy experiments tracking the changes in the morphology of a solid DDF sample. Then, we complemented the formal macroscopic kinetics with some mechanistic patterns of the primary decomposition channels from quantum chemical calculations. The three reactions involving all important moieties of the DDF molecule turned out to compete very closely: viz., the nitro-nitrite isomerization, radical C(heterocycle)-N(bridge) bond scission and molecular decomposition comprised of the consequent N-O and C-C bond scissions in a furoxane ring. The DLPNO-CCSD(T) activation barriers of all these reactions were close to ∼230 kJ mol−1. Most importantly, the calculations provide some mechanistic details missing in thermoanalytical experiment and formal kinetic models. Apart from this, we also determined a mutually consistent set of thermochemical and phase change data for DDF.

AB - Novel energetic materials (EM) often combine two intrinsically counter trends, viz., a high energy density and mediocre safety parameters, like thermal stability and sensitivity toward mechanical stimuli. A rational design of promising EMs requires a proper understanding of their thermal stability at both macroscopic and molecular levels. In the present contribution, we studied in detail the thermal stability of 4,4′-dinitro-3,3′-diazenofuroxan (DDF), an ultrahigh-performance energetic material with a reliable experimental detonation velocity being very close to 10 km s−1. To this end, we employed a set of complementary thermoanalytical (DSC and TGA in the solid state along with advanced thermokinetic models, optical microscopy, and gas products detection) and theoretical techniques (DLPNO-CCSD(T) quantum chemical calculations). According to the DSC measurements, the solid-state thermolysis of DDF turned out to be a complex three-step process. The decomposition commences at ∼85 °C and the most intense heat release occurs at ∼130 °C depending on the heating rate. In order to properly describe the kinetics of DDF thermolysis beyond the simple Kissinger and Friedman methods, we applied a “top-down” kinetic approach resulting in the formal model comprised of three independent stages. A flexible Kolmogorov-Johnson-Mehl-Avrami-Erofeev equation was applied for the first decomposition stage along with the extended Prout-Tompkins equation for the second and third processes, respectively. The formal exponent in the former equation turned out to be close to a second order, thus suggesting a two-dimensional nuclei-growth model for the first stage. We rationalized this fact with the aid of optical microscopy experiments tracking the changes in the morphology of a solid DDF sample. Then, we complemented the formal macroscopic kinetics with some mechanistic patterns of the primary decomposition channels from quantum chemical calculations. The three reactions involving all important moieties of the DDF molecule turned out to compete very closely: viz., the nitro-nitrite isomerization, radical C(heterocycle)-N(bridge) bond scission and molecular decomposition comprised of the consequent N-O and C-C bond scissions in a furoxane ring. The DLPNO-CCSD(T) activation barriers of all these reactions were close to ∼230 kJ mol−1. Most importantly, the calculations provide some mechanistic details missing in thermoanalytical experiment and formal kinetic models. Apart from this, we also determined a mutually consistent set of thermochemical and phase change data for DDF.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85210113816&origin=inward&txGid=eb4aed78464ba85e7b8be3c3564502ae

UR - https://www.mendeley.com/catalogue/81653a67-0ab1-38de-b146-aff8d4932807/

U2 - 10.1039/d4cp02836h

DO - 10.1039/d4cp02836h

M3 - Article

C2 - 39584567

VL - 26

SP - 29541

EP - 29551

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 47

ER -