The Journal of Physical Chemistry A · 2009 · 50 citations · 17 references
Natural SciencesMaterials EngineeringMaterials ScienceEnergy MaterialsThermal AnalysisThermodynamicsChemical ThermodynamicsDecomposition AnalysisDecomposition ProcessesHigh-pressure ProcessingHigh-pressure ThermodynamicsNucleationAutocatalysisDecomposition KineticsDecomposition MechanismsDegradation KineticsPressure-dependent KineticsTemperature Effects On DecompositionThermal DecompositionThermal Decomposition Reactions
The effect of pressure on the global thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Global decomposition rates were determined by fitting the fraction reacted to the extended-Prout-Tompkins nucleation-growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low-to-moderate pressures (i.e., between ambient pressure and 0.1 GPa) and decelerates the decomposition at higher pressures. The decomposition acceleration is attributed to pressure-enhanced autocatalysis, whereas the deceleration at high pressures is attributed to pressure-inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both the beta- and delta-polymorphs of HMX are sensitive to pressure in the thermally induced decomposition kinetics.
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Physical chemistry: a molecular approach
Choice Reviews Online · 1998 · 1.1K citations
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Global Kinetic Analysis of Complex Materials
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Natural Sciences, Materials Science, Petroleum Engineering +17