Adding amines to liquid nitromethane (NM) is known to lower the threshold for the shock-to-detonation transition because amines catalyze proton transfer reactions that are the initial steps in the energy release process. We studied NM with 1 wt % ethylenediamine (NM/EDA) with 4 ns input shocks using time and space resolved diagnostics: photon Doppler velocimetry (PDV), optical pyrometry, and nanosecond video imaging. The 4 ns shocks are fast enough to time-resolve the reaction kinetics and the shock-to-detonation transition. We find that it is possible to shock ignite the NM/EDA without producing a detonation, so there is more to amine sensitization of the shock-to-detonation process than simply lowering the barrier to initial reactions. We find that although 1 wt % EDA has little effect on the ambient properties of NM, it dramatically alters the Hugoniot. The shock speed in NM/EDA is reduced, indicating that shocked NM/EDA is significantly more compressible than NM. Higher compressibility is associated with greater adiabatic heating, so EDA both lowers the barrier to proton transfer reactions and increases shock energy absorption. To explain the enhanced compressibility, we propose that shocking NM/EDA produces a reactive flow that has a much higher ionic strength than in NM. The sudden transformation from a molecular liquid to an ionic liquid with stronger intermolecular interactions is responsible for enhanced compressibility and shock heating.
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http://dx.doi.org/10.1021/acs.jpcb.1c04427 | DOI Listing |
Shock and detonation velocities are today measured continuously using long silica chirped fiber Bragg gratings (CFBGs). These thin probes can be directly inserted into high-explosive samples. The use of a polymer fiber increases the sensitivity at low pressure levels when studying, for instance, shock-to-detonation transitions in wedge tests.
View Article and Find Full Text PDFJ Phys Chem A
September 2021
Combustion Research Facility, Sandia National Laboratories, Livermore, California 94550, United States.
The coupling of inter- and intramolecular vibrations plays a critical role in initiating chemistry during the shock-to-detonation transition in energetic materials. Herein, we report on the subpicosecond to subnanosecond vibrational energy transfer (VET) dynamics of the solid energetic material 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) by using broadband, ultrafast infrared transient absorption spectroscopy. Experiments reveal VET occurring on three distinct time scales: subpicosecond, 5 ps, and 200 ps.
View Article and Find Full Text PDFJ Phys Chem B
July 2021
School of Chemical Sciences, University of Illinois Urbana-Champaign, Urbana, Illinois 61801, United States.
Adding amines to liquid nitromethane (NM) is known to lower the threshold for the shock-to-detonation transition because amines catalyze proton transfer reactions that are the initial steps in the energy release process. We studied NM with 1 wt % ethylenediamine (NM/EDA) with 4 ns input shocks using time and space resolved diagnostics: photon Doppler velocimetry (PDV), optical pyrometry, and nanosecond video imaging. The 4 ns shocks are fast enough to time-resolve the reaction kinetics and the shock-to-detonation transition.
View Article and Find Full Text PDFSensors (Basel)
February 2020
CEA, DAM, GRAMAT, BP 80200, F-46500 Gramat, France.
Dynamic measurements of shock and detonation velocities are performed using long chirped fiber Bragg gratings (CFBGs). Such thin probes, with a diameter of typically 125 µm or even 80 µm can be directly inserted into high-explosive (HE) samples or simply glued laterally. During the detonation, the width of the optical spectrum is continuously reduced by the propagation of the wave-front, which physically shortens the CFBG.
View Article and Find Full Text PDFJ Phys Chem A
October 2018
Sandia National Laboratories , Livermore , California 94550 , United States.
The chemical and physical processes involved in the shock-to-detonation transition of energetic solids are not fully understood due to difficulties in probing the fast dynamics involved in initiation. Here, we employ shock interferometry experiments with sub-20-ps time resolution to study highly textured (110) pentaerythritol tetranitrate (PETN) thin films during the early stages of shock compression using ultrafast laser-driven shock wave methods. We observe evidence of rapid exothermic chemical reactions in the PETN thin films for interface particle velocities above ∼1.
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