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Energy Transfer between Coherently Delocalized States in Thin Films of the Explosive Pentaerythritol Tetranitrate (PETN) Revealed by Two-Dimensional Infrared Spectroscopy

Journal of Physical Chemistry B

Ostrander, Joshua S.; Knepper, Robert; Tappan, Alexander S.; Kay, Jeffrey J.; Zanni, Martin T.; Farrow, Darcie F.

Pentaerythritol tetranitrate (PETN) is a common secondary explosive and has been used extensively to study shock initiation and energy propagation in energetic materials. We report 2D IR measurements of PETN thin films that resolve vibrational energy transfer and relaxation mechanisms. Ultrafast anisotropy measurements reveal a sub-500 fs reorientation of transition dipoles in thin films of vapor-deposited PETN that is absent in solution measurements, consistent with intermolecular energy transfer. The anisotropy is frequency dependent, suggesting spectrally heterogeneous vibrational relaxation. Cross peaks are observed in 2D IR spectra that resolve a specific energy transfer pathway with a 2 ps time scale. Transition dipole coupling calculations of the nitrate ester groups in the crystal lattice predict that the intermolecular couplings are as large or larger than the intramolecular couplings. The calculations match well with the experimental frequencies and the anisotropy, leading us to conclude that the observed cross peak is measuring energy transfer between two eigenstates that are extended over multiple PETN molecules. Measurements of the transition dipole strength indicate that these vibrational modes are coherently delocalized over at least 15-30 molecules. We discuss the implications of vibrational relaxation between coherently delocalized eigenstates for mechanisms relevant to explosives.

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TYPE Conference Poster YEAR 2017
ScopusOSTIDOI

Near-failure detonation behavior of vapor-deposited hexanitrostilbene (HNS) films

AIP Conference Proceedings

Knepper, Robert; Wixom, Ryan R.; Marquez, Michael P.; Tappan, Alexander S.

Hexanitrostilbene (HNS) films were deposited onto polycarbonate substrates using vacuum thermal sublimation. The deposition conditions were varied in order to alter porosity in the films, and the resulting microstructures were quantified by analyzing ion-polished cross-sections using scanning electron microscopy. The effects of these changes in microstructure on detonation velocity and the critical thickness needed to sustain detonation were determined. The polycarbonate substrates also acted as recording plates for detonation experiments, and films near the critical thickness displayed distinct patterns in the dent tracks that indicate instabilities in the detonation front when approaching failure conditions.

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TYPE Conference Poster YEAR 2017
ScopusOSTI

Geometry effects on detonation in vapor-deposited hexanitroazobenzene (HNAB)

AIP Conference Proceedings

Tappan, Alexander S.; Wixom, Ryan R.; Knepper, Robert

Physical vapor deposition is a technique that can be used to produce explosive films with controlled geometry and microstructure. Films of the high explosive hexanitroazobenzene (HNAB) were deposited by vacuum thermal evaporation. HNAB deposits in an amorphous state that crystallizes over time into a polycrystalline material with high density and a consistent porosity distribution. In previous work, we evaluated detonation critical thickness in HNAB films in an effectively infinite slab geometry with insignificant side losses. In this work, the effect of geometry on detonation failure was investigated by performing experiments on films with different thicknesses, while also changing lateral dimensions such that side losses became significant. The experimental failure thickness was determined to be 75.5 μm and 71.6 μm, for 400 μm and 1600 μm wide HNAB lines, respectively. It follows from this that the minimum width to achieve detonation behavior representing an infinite slab configuration is greater than 400 μm.

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TYPE Conference Poster YEAR 2017
ScopusOSTI

Spectroscopic analysis of time-resolved emission from detonating thin film explosive samples

AIP Conference Proceedings

Kay, Jeffrey J.; Wixom, Ryan R.; Jilek, Brook A.; Knepper, Robert; Tappan, Alexander S.; Damm, David L.

We report a series of time-resolved spectroscopic measurements that aim to characterize the reactions that occur during shock initiation of high explosives. The experiments employ time-and wavelength-resolved emission spectroscopy to analyze light emitted from detonating thin explosive films. This paper presents analysis of optical emission spectra from hexanitrostilbene (HNS) and pentaerythritol tetranitrate (PETN) thin film samples. Both vibrationally resolved and broadband emission features are observed in the spectra and area as electronic transitions of intermediate species.

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TYPE Conference Poster YEAR 2017
ScopusOSTIDOI

An evaluation of complementary approaches to elucidate fundamental interfacial phenomena driving adhesion of energetic materials

Journal of Colloid and Interface Science

Hoss, Darby J.; Knepper, Robert; Hotchkiss, Peter J.; Tappan, Alexander S.; Boudouris, Bryan W.; Beaudoin, Stephen P.

Cohesive Hamaker constants of solid materials are measured via optical and dielectric properties (i.e., Lifshitz theory), inverse gas chromatography (IGC), and contact angle measurements. To date, however, a comparison across these measurement techniques for common energetic materials has not been reported. This has been due to the inability of the community to produce samples of energetic materials that are readily compatible with contact angle measurements. Here we overcome this limitation by using physical vapor deposition to produce thin films of five common energetic materials, and the contact angle measurement approach is applied to estimate the cohesive Hamaker constants and surface energy components of the materials. The cohesive Hamaker constants range from 85 zJ to 135 zJ across the different films. When these Hamaker constants are compared to prior work using Lifshitz theory and nonpolar probe IGC, the relative magnitudes can be ordered as follows: contact angle > Lifshitz > IGC. Furthermore, the dispersive surface energy components estimated here are in good agreement with those estimated by IGC. Due to these results, researchers and technologists will now have access to a comprehensive database of adhesion constants which describe the behavior of these energetic materials over a range of settings.

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TYPE Journal Article YEAR 2016
ScopusOSTIDOI
Results 51–75 of 107
Results 51–75 of 107