Issue 15, 2018

Examining the chemical and structural properties that influence the sensitivity of energetic nitrate esters

Abstract

The sensitivity of explosives is controlled by factors that span from intrinsic chemical reactivity and chemical intramolecular effects to mesoscale structure and defects, and has been a topic of extensive study for over 50 years. Due to these complex competing chemical and physical elements, a unifying relationship between molecular framework, crystal structure, and sensitivity has yet to be developed. In order to move towards this goal, ideally experimental studies should be performed on systems with small, systematic structural modifications, with modeling utilized to interpret experimental results. Pentaerythritol tetranitrate (PETN) is a common nitrate ester explosive that has been widely studied due to its use in military and commercial explosives. We have synthesized PETN derivatives with modified sensitivity characteristics by substituting one –CCH2ONO2 moiety with other substituents, including –CH, –CNH2, –CNH3X, –CCH3, and –PO. We relate the handling sensitivity properties of each PETN derivative to its structural properties, and discuss the potential roles of thermodynamic properties such as heat capacity and heat of formation, thermal stability, crystal structure, compressibility, and inter- and intramolecular hydrogen bonding on impact sensitivity. Reactive molecular dynamics (MD) simulations of the C/H/N/O-based PETN-derivatives have been performed under cook-off conditions that mimic those accessed in impact tests. These simulations infer how changes in chemistry affect the subsequent decomposition pathways.

Graphical abstract: Examining the chemical and structural properties that influence the sensitivity of energetic nitrate esters

Supplementary files

Article information

Article type
Edge Article
Submitted
25 Feb 2018
Accepted
08 Mar 2018
First published
09 Mar 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2018,9, 3649-3663

Examining the chemical and structural properties that influence the sensitivity of energetic nitrate esters

Virginia W. Manner, M. J. Cawkwell, E. M. Kober, T. W. Myers, G. W. Brown, H. Tian, C. J. Snyder, R. Perriot and D. N. Preston, Chem. Sci., 2018, 9, 3649 DOI: 10.1039/C8SC00903A

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