Thermodynamics Research Center / ThermoML | Thermochimica Acta

HP-DSC study of energetic materials. Part I. Overview of pressure influence on thermal behavior

Muravyev, N. V.[Nikita V.], Monogarov, K. A.[Konstantin A.], Bragin, A. A.[Anatoly A.], Fomenkov, I. V.[Igor V.], Pivkina, A. N.[Alla N.]
Thermochim. Acta 2016, 631, 1-7
ABSTRACT
High pressure differential scanning calorimetry (HP-DSC) has been used to study thermal decomposition of energetic materials, i.e., trinitrotoluene, cyclotrimethylenetrinitramine, and ammonium dinitramide. HP-DSC runs have been performed in the range of 0.1.14 MPa both in inert and oxidative environments to determine the effect of pressure on vaporization/dissociation, melting, and decomposition processes. Results reveal that the melting point linearly increase with pressure with the slope 0.12.0.15.C/MPa. Decomposition pathways and DSC effects are highly affected by pressure, as evaluated by changes in the peak temperature, reaction heat effect, and kinetic parameters. Activation energy and pre-exponential factor values were defined for separated decomposition stages of compounds, and found to vary with pressure. Vaporization/dissociation of starting material along with secondary reactions are proposed to be the main processes affected by pressure. Obtained results reveal that HP-DSC technique is useful in determining kinetic parameters and heat effect under elevated pressures, where energetic materials are usually applied.
Compounds
# Formula Name
1 C3H6N6O6 1,3,5-triaza-1,3,5-trinitrocyclohexane
2 H4N4O4 ammonium dinitramide
3 C7H5N3O6 2,4,6-trinitrotoluene
Datasets
The table above is generated from the ThermoML associated json file (link above). POMD and RXND refer to PureOrMixture and Reaction Datasets. The compound numbers are included in properties, variables, and phases, if specificied; the numbers refer to the table of compounds on the left.
Type Compound-# Property Variable Constraint Phase Method #Points
  • POMD
  • 1
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 1
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 1
  • Vapor or sublimation pressure, kPa ; Crystal
  • Temperature, K; Crystal
  • Crystal
  • Liquid
  • DSC
  • 5
  • POMD
  • 2
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 2
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 2
  • Vapor or sublimation pressure, kPa ; Crystal
  • Temperature, K; Crystal
  • Crystal
  • Liquid
  • DSC
  • 8
  • POMD
  • 3
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 3
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 3
  • Vapor or sublimation pressure, kPa ; Crystal
  • Temperature, K; Crystal
  • Crystal
  • Liquid
  • DSC
  • 5