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Study of Chemical Micro-Mechanism of the Energetic Materials Initiation by Means of Characteristics of their Thermal Decomposition.
Authors: Zeman Svatopluk
Year: 2006
Type of publication: článek ve sborníku
Name of source: CD-Proceedings of the 34th Annual Conference NATAS
Publisher name: North American Thermal Analysis Society
Place: N
Page from-to: 1-12
Titles:
Language Name Abstract Keywords
cze Studium chemického mikromechanizmu iniciace energetických materiálů pomocí charakteristik jejich tepelného rozkladu Přehled autorových výsledků ze studia chemického mikromechanizmu iniciace energetických materiálů za posledních 27 let s využitím DTA (aplikace metod Pylojanovy a Kissingerovy vyhodnocení DTA-záznamů) a v návaznosti 15N NMR spektroskopie a výpočtových metod nábojů na dusících klíčových atomů reakčního centra molekuly. Zdůvodněna modifikace a použití Evans-Polanyi-Semenovovy rovnice v tomto studiu. Použitými postupy a metodami zdůvodněna totožnost primárních štěpných procesů v iniciaci mechanickými podněty a elektrickou jiskrou s těmiže procesy nízkoteplotní tepelné dekompozice energetických materiálů., aktivační energie, DTA, elektronový náboj, výbušiny, iniciace, chemický mechanizmus, 15N NMR chemické posuny, polynitroareny
eng Study of Chemical Micro-Mechanism of the Energetic Materials Initiation by Means of Characteristics of their Thermal Decomposition. The paper presents a survey of the most important results published by the author in the field of differential thermal analysis (DTA) and the Russian vacuum manometrical method (SSM) applied to studies of chemical micro-mechanism of initiation of energetic materials (EMs). Characteristics of thermal reactivity of EMs, resulted from evaluation of the outputs of their DTA measurements by the Piloyan and Kissinger methods, correlate with the detonation characteristics of these materials. Similarly, through the modified Evans-Polanyi-Semenov equation also activation energies, Ea, from the SMM application correlate with square of detonation velocities or heats of explosion of the EMs. For specification of reaction centre of the initiation in the molecules of polynitro arenes and nitramines the 15N NMR chemical shifts, N, of the nitrogen atoms of the primarily reacting nitro groups and calculated charges, qN, on these nitrogen atoms are used. The specification is realized on the basis of relationships between the N, and qN values, on the one hand, and thermal reactivity and detonation characteristics, on the other. On the basis of the results obtained, particularly the discussion of modified E-P-S equation, it is stated that the primary fission processes of EMs molecules in the low-temperature thermal decomposition should be identical with those in their initiations by mechanical stimuli. Also it is stated that the primary chemical fragmentation of these materials in their detonation proceeds already during their compression by shock or detonation wave, i. e. at milder conditions than are those present at the front of detonation wave or in its reaction zone and, therefore, the detonation transformation itself should be preceded by an induction period. activation energy, DTA, electron charges, explosives, initiation, chemical mechanism, nitramines, 15N NMR chemical shift, polynitro arenes

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