The thermal decomposition of explosives. Part II. Cyclotrimethylenetrinitramine and cyclotetramethylenetetranitramine

Robertson, A. J. B.

doi:10.1039/tf9494500085

Cited by 134 publications

(44 citation statements)

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“…Comparison of the kinetic parameters of heat release in the condensed phase of HMX (points 1) and HMX decomposition in the nitrobenzene solution (curve 2[49]), acetone (curve 3[50]), and melt (curves 4[51] and 5[52]). …”

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confidence: 99%

Mechanism of HMX combustion in a wide range of pressures

Sinditskii

Egorshev

Berezin

et al. 2009

Combust Explos Shock Waves

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Data obtained in the present work and available publications on combustion of cyclotetramethylene tetranitramine (HMX) at different initial temperatures are analyzed. The temperature sensitivity of the HMX burning rate is demonstrated to increase with increasing initial temperature at pressures of 0.1 to 10 MPa, which is typical for combustion of substances with the leading reaction in the condensed phase (c-phase model). Experimental values of the temperature sensitivity of the burning rate in the pressure interval between 0.1 and 1 MPa are higher than the values predicted by the c-phase model, but this fact indicates the transition of the combustion process to another regime rather than the combustion instability in this area. The flame structure of burning HMX with different additives is studied with the help of thin tungstenrhenium thermocouples in the pressure range from 0.025 to 1 MPa. The gas-phase flame is found to ignite in an inductive mode, at least up to a pressure of 1 MPa. The surface temperature is obtained as a function of pressure on the basis of experimental data in a wide range of pressures: ln p = −14,092/T + 21.72 (p in atm). Two possible reasons for the oscillatory regime of HMX combustion observed at atmospheric pressure are proposed: the emergence of resonance phenomena during combustion of an inhomogeneous gas mixture in the tube and the lack of correspondence between the chemical reaction rate in the gas phase at the instant of the resonance and its energy capabilities, which do not allow a necessary HMX gasification rate to be ensured. A mechanism of HMX combustion is proposed, which offers an adequate description in a wide range of pressures up to 10 MPa. The mechanism is based on the leading role of HMX decomposition in the melt at the surface temperature.

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confidence: 99%

Mechanism of HMX combustion in a wide range of pressures

Sinditskii

Egorshev

Berezin

et al. 2009

Combust Explos Shock Waves

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“…Thus, RDX molecules dissociate according to pathways that are determined both by concerted symmetrical triple ®ssion and by N±N bond scission. It is still disputable whether these reactions control the decomposition of RDX and HMX in the condensed phase and whether reactions between adjacent molecules are important, as was originally suggested by Robertson (5) . The temperature dependence of formation rates for the gaseous products released during the pyrolysis of HMX was determined by simultaneous thermogravimetric modulated beam mass spectrometry (9) .…”

Section: Computer Modeling Experimental Data Results and Discussionmentioning

confidence: 97%

“…Robertson (5) originally proposed elimination of formaldehyde as the initial step of decomposition in solution. His results showed that such decomposition displays monomolecular behavior, whereas pure RDX and HMX exhibited the effect of neighboring molecules.…”

Section: Computer Modeling Experimental Data Results and Discussionmentioning

confidence: 99%

Computer Modeling of Probable Decomposition Reactions: Cyclonitramines

Pivina

Sokerina

Lushnikov

et al. 1999

Propellants, Explosives, Pyrotechnics

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SummaryAn approach to computer synthesis and retrosynthesis of organic compounds was formulated, and the CASB (Computer-Assisted Structure Building) software for its computer implementation was created. The approach was evaluated by the example of computer generation of probable routes for reactions of homolytic decomposition. Elementary steps of homolysis reactions were modeled with the use of the``retrosynthetic'' method. Each elementary reaction describes fragments that should be present in the structure and structural modi®cations that should be carried out to obtain reaction products. Target fragments are described in terms of production rules by specifying types of atoms, their formal charges and radical states, numbers of adjacent heteroatoms, hybridizations, etc. All possible intermediates of molecular homolysis reactions are generated by the program in a single step and then used in further search for probable pathways of decomposition during subsequent steps until the given maximum number of steps is achieved. Screening of advantageous pathways for these reactions was based on a set of empirical rules. The results obtained by the suggested approach and the corresponding program were illustrated by the example of some cyclic nitramines (RDX and HMX) and demonstrated good agreement with the experiment.

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“…Arrhenius expressions for the temperature effect on the rate constant have been cited for thermal decomposition of HMX in the solid -phase Medvedev, 1977) and in the liquid phase " to be published; Robertson, 1949). Fol-"lowing is an expression for the rate constant which is applicable to both solid and liquid phase thermal decomposition of IMX:…”

Section: Hmmentioning

confidence: 99%

“…The e. following are expressions for the rate constant (k) : A number of kinetic studies have been performed on the thermal decomposition of RDX. The rate of thermal decomposition of RDX has been shown to follow first order kinetics (Schroeder --to be published;Urbanski, 1964;Robertson, 1949) although complex kinetics may be observed under some conditions (Schroeder, 1979;Schroeder --to be published).…”

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confidence: 99%