Mass spectrometric study of the thermal decomposition of ammonium perchlorate
01 Jan 1964-Transactions of The Faraday Society (The Royal Society of Chemistry)-Vol. 60, pp 1783-1791
About: This article is published in Transactions of The Faraday Society.The article was published on 1964-01-01. It has received 51 citations till now. The article focuses on the topics: Ammonium perchlorate & Thermal decomposition.
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TL;DR: In this paper, the catalytic pyrolysis of hydroxyl terminated polybutadiene (HTPB) binder in composite propellant by free-standing CuO nanoparticles synthesized through a novel aqueous thermolysis synthetic route was reported.
30 citations
TL;DR: In this article, an analysis of the kinetics of thermal decomposition was made using a model fitting procedure as well as an isoconversional method, independent of any model.
Abstract: Bis(propylenediamine)metal perchlorate (BPMP) complexes like [M(pn)2](ClO4)2 (where M=Cr, Mn, Ni, Cu, Zn and pn=propylenediamine) have been prepared and characterized by gravimetric methods, infrared and elemental analysis. Thermal properties have been studied using simultaneous thermogravimetry-differential thermal analysis in atmospheres of nitrogen and air to examine the effect of atmospheric change on thermal decomposition of these complexes. Changing of the atmosphere does not cause any measurable changes in the decomposition of complexes. However, as indicated by thermoanalytical techniques, the thermal stability of present complexes decreases in the order: [Cr(pn)2](ClO4)2>[Mn(pn)2](ClO4)2>[Zn(pn)2](ClO4)2>[Ni(pn)2](ClO4)2>[Cu(pn)2](ClO4)2. Isothermal thermogravimetry, over the temperature range of decomposition has been done for all the complexes. An analysis of the kinetics of thermal decomposition was made using a model fitting procedure as well as an isoconversional method, independent of any model. The results of both kinetic approaches have been discussed critically. The explosion delay (DE) was measured to investigate the trend of rapid thermal analysis.
28 citations
TL;DR: In this article, the authors studied 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.
Abstract: 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 ksub.= 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 t...
26 citations
01 Jan 2008
TL;DR: In terms of publications, ammonium perchlorate (AP) has been the most extensively investigated solid oxidizer since its introduction into propellants, probably in the late 1940s by the Jet Propulsion Laboratory as discussed by the authors.
Abstract: W ORLDWIDE, ammonium perchlorate (AP, NH^CIC^) and hydroxylterminated-polybutadiene (HTPB) composite mixtures, usually also containing aluminum powder and ballistic modifiers, are the most frequently used formulations in solid rocket propellants. In terms of publications, AP has been the most extensively investigated solid oxidizer since its introduction into propellants, probably in the late 1940s by the Jet Propulsion Laboratory. A large number of publications appeared in 1950-1970, and, by comparison, a relatively lesser number have appeared since then. The impressive review by Jacobs and Whitehead was quite extensive in range and depth at the time of publication in 1969. The falloff in research interest after this time is reflected in the additional information reviewed 10-15 years later, but subsequent reviews of various aspects of decomposition, ignition, and combustion" of AP-composite propellants have appeared. A modest resurgence of new interest in AP-composite propellant decomposition and combustion is motivated in part by the availability of advanced methods of diagnostics," by new kinetics data and methods of modeling," and by intriguing plateau-burning behavior of some AP-HTPB formulations.' Despite the widespread use and long investigative history of AP-fuel mixtures, it still can be said that AP alone and AP-fuel composites remain among the most confounding materials in the research setting. From the point of view of chemistry, one reason is that the full range of formal oxidation states of nitrogen and chlorine can apparently become involved, for example, the formal oxidation state of Cl in C1O4 is +7, whereas that of HC1 is -1; N in NHj is -3, whereas that of N in NOj (Ref. 19) and HNO3 (Ref. 20) is +5. When all of the various combinations of
26 citations
TL;DR: In this paper, the authors investigated the mechanism of composite propellant ageing and found that the rate-controlling step lies in the oxidiser decomposition or in the binder decomposition.
25 citations