Investigation of Solid Propellant Decomposition Characteristics and Their Relation to Observed Burning Rates

Feinauer, L. R.; Waesche, R. H. Woodward; Wenograd, Joseph

doi:10.2514/6.1967-1515

Cited by 17 publications

(5 citation statements)

References 9 publications

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“…By adding the heats of reaction of −, we get the enthalpy change for the reaction NH 4 ClO 4 (s) → NH 3 (g) + HOClO 3 (g), which is 44.9 and 44.1 kcal/mol at the CCSD(T)/6−311+G(3df, 2p)//B3LYP/6−311+G(3df,2p) and B3LYP/6−311+G(3df,2p) levels, respectively, which are in excellent agreement with the values mentioned above and with the value of 45.0 kcal/mol predicted by Politzer and Lane. The calculated data lie between the experimental values 30.6 kcal/mol, obtained by the differential scanning calorimetry (DSC) method, and 58 ± 2 kcal/mol, obtained by the transpiration method.…”

Section: Resultssupporting

confidence: 60%

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Mechanism and Kinetics for Ammonium Perchlorate Sublimation: A First-principles Study

Zhu

Lin

2008

J. Phys. Chem. C

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We have studied for the first time the kinetics and mechanism for the sublimation/decomposition of NH4ClO4 by first-principles calculations, using a generalized gradient approximation with the plane-wave density functional theory. Supercells containing 4, 8, and 16 NH4ClO4 units were used; the predicted enthalpic change for solid NH4ClO4 to gaseous NH3 and HClO4 is 45.0 ± 1.5 kcal/mol. The calculated desorption activation energies for NH3, HClO4, and H3N···HOClO3 molecular complexes, individually, from the relaxed surface are 45.3, 43.5, and 28.1 kcal/mol, respectively. The rate constant for the dominant sublimation process desorbing H3N···HOClO3 as a pair can be presented by k sub.= 6.53 × 1012 exp (−28.8 kcal/mol/RT) s−1, which is in reasonable agreement with available experimental data. Expectably, the decomposition of H3N···HOClO3 (g) to NH3 (g) and HOClO3 (g) is considerably faster, about 1 × 107 times greater than that for the sublimation process in the same temperature range. The rate constant for the gas-phase dissociation step can be expressed by 1.20 × 1015 exp (−14.6 kcal/mol/RT) sec−1. This study further confirms that the activation energy for the sublimation of an ammonium salt is significantly lower than the enthalpic change and that the molecular complex of acid and base sublimes concurrently as a pair.

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Section: Resultssupporting

confidence: 60%

“…2 The calculated data lie between the experimental values 30.6 kcal/mol,24 obtained by the differential scanning calorimetry (DSC) method, and 58 ( 2 kcal/mol,25 obtained by the transpiration method.3.3. Sublimation Energies of NH 3 , HClO 4 , and H 3 N • • • HOClO…”

mentioning

confidence: 67%

Mechanism and Kinetics for Ammonium Perchlorate Sublimation: A First-principles Study

Zhu

Lin

2008

J. Phys. Chem. C

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“…This would suggest that the exothermic decomposition of ammonium perchlorate plays an important role. This observation is at least consistent with the theoretical calculations of Hermance 23 -26 and with the experimental data obtained by Waesche et al 27 If R is negative, the shift in frequency at which the maximum response occurs when coated oxidizer is used suggests that the coatings reduce the over-all activation energy of the surface pyrolysis reactions. A reduction in E 2 reduces both the parameters R and S. If R is then negative, Fig.…”

Section: Comparison Of Experiments and Theorysupporting

confidence: 90%

Surface reaction effects on the acoustic response of composite solidpropellants.

1968

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The contribution of pressure-sensitive interfacial reactions to the acoustic admittance of composite solid propellants has been studied experimentally and theoretically. Using a carboxy-terminated poly butadiene-ammonium perchlorate propellant, the effects of various coatings on the oxidizer crystals were investigated with a T-burner over a range of frequencies from 150 to 5000 cps. The results show that, of the coatings used (Kel-F 800, Hypalon 30, Viton A, and ethyl-cellulose), only the Kel-F and Viton reduced the apparent reactivity of the propellant binder-oxidizer interface sufficiently to produce a significant reduction in the maximum value of the observed acoustic admittance. These effects are consistent with the greater resistance to oxidation of Kel-F and Viton A compared to the other coating materials and the basic propellant binder. However, all of the coatings produced a significant shift in the acoustic frequency at which the maximum admittance is observed, even when burning rate changes are considered. Theoretical studies were conducted using a combustion model that incorporates the effects of pressure-dependent surface reactions, pressure-dependent gas-phase heat transfer, and surface pyrolysis reactions. The predicted acoustic admittance frequency relation is characterized by three independent parameters using a perturbation approach. Parametric studies reveal that high ratios of the maximum acoustic response function to the burning rate pressure exponent are predicted when the net heat release at the propellant surface (pressure-dependent reactions plus pyrolysis reactions) is nearly zero or is exothermic. The stability of the combustion process in self-excited modes has also been considered theoretically and the stability bounds determined as a function of combustion parameters. Nomenclature ai= I + a 1 c = sonic velocity of the combustion gases EI = activation energy of exothermic surface reactions Ei = activation energy of over-all pyrolysis rate at surface Ez = activation energy of solid-phase combustion reactions Ef = activation energy of gas-phase reactions g , fd =. frequency of the acoustic pressure oscillations at the point where a g and ad were measured FQ = steady-state heat flux from gas-phase combustion zone to solid surface F = instantaneous heat flux from gas-phase combustion zone to solid surface k = thermal conductivity mi =-}[! + (! + s)i"] m l = order of gas-phase reaction n = steady-state burning rate exponent n l -pressure exponent on gas-phase heat flux P = instantaneous pressure PO = steady-state pressure P = amplitude of the acoustic pressure oscillation r = instantaneous linear burning rate of propellant r 0 = steady-state linear burning rate of propellant f = amplitude of the burning rate oscillations R = (/3 La Placiaii variable time temperature steady-state temperature propellant flame temperature initial temperature of the propellant distance into the solid from the surface Arrhenius pre-exponential factor for exothermic surface reactions Arrhenius pre-exponential fac...

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“…Waesche et al 36 studied the decomposition (by DSC technique) and combustion behavior of PBAA/AP propellants. The results show that those formulations that increase r also cause the major exotherms to occur at lower temperatures and with faster rates.…”

Section: B) Condensed-phase Theoriesmentioning

confidence: 99%

“…Waesche et al 36 have studied the thermal decomposition and burning rate of polybutadiene-acrylic acid (PBAN) based propellants. The studies were carried out at ambient pressure and 250 psi to examine the effect of particle size and catalysts.…”

Section: Combustion Of Composite Solid Propellantsmentioning

confidence: 99%

Comprehensive view of the combustion models of composite solid propellants

Kishore

1979

AIAA Journal

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Investigation of Solid Propellant Decomposition Characteristics and Their Relation to Observed Burning Rates

Cited by 17 publications

References 9 publications

Mechanism and Kinetics for Ammonium Perchlorate Sublimation: A First-principles Study

Mechanism and Kinetics for Ammonium Perchlorate Sublimation: A First-principles Study

Surface reaction effects on the acoustic response of composite solidpropellants.

Comprehensive view of the combustion models of composite solid propellants

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