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Kinetics and mechanism of the low-energy β-a phase transition of the second kind in 2,4-dinitroanisole

Defence Technology（防务技术） 2024年第10期40卷 210-224页

作者： Aleksandr V.Stankevich Nikolay A.Rasputin Anisa KhRudina Gennady L.Rusinov vera i.filyakova Valery N.Charushin i.Ya. Postovsky institute of Organic Synthesis Ural Branch of the Russian Academy of Sciencesekaterinburg 620108russia Russian Federal Nuclear Center-Zababakhin All-Russia Research institute of Technical Physics snezhinsk 456770russia Kazan National Research Technological University kazan 420015russia

in this work, comprehensive studies of 2,4-dinitroanisole(2,4DNAN) were carried out using powder thermorentgenography of the internal standard. The time of the complete polymorphic transition in the solid phase β→a in 2,4DNAN under various combinations of conditions has been determined. it has been established that, regardless of the season of manufacture of the substance, when it is stored for 8-9months, with a change in ambient temperature from minus 30℃ to plus 30℃, a complete polymorphic transition β→a occurs. When stored in conditions below minus 5℃, polymorphic transition does not occur. When stored in conditions above plus 30℃ in a closed container, polymorphic transition occurs within 3 weeks. The polymorphic transition is accompanied by a decrease in density by 1.3%-1.5% and an increase in melting temperature by 10-12℃, depending on the degree of purity of the starting substance. The activation energy of the molecular rearrangement was 68-70 k J/mol(16.5 ± 3 kcal/mol). The mechanism of polymorphic transition has been evaluated, which is presumably based on internal homodiffusion and energy transfer to the surface of the mass of powder particles and the product. The average activation energy of the polymorphic transition process was 110 ± 6.2 k J/mol(26.2 kcal/mol). in an open container, reactions proceed by a homogeneous mechanism, and in a closed container by a heterogeneous mechanism involving the gas phase.

关键词： Energetic materials Melt-castable 2,4-Dinitroanisole Polymorphic transition Kinetics Mechanism Homodiffusion Sublimation

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