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All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Photoactive High Explosives: Substituents Effects on Tetrazine Photochemistry and Photophysics

High explosives that are photoactive, i.e., can be initiated with light, offer significant advantages in reduced potential for accidental electrical initiation. In this study, we examined a series of structurally related tetrazine based photoactive high explosive materials to detail their photochemical and photophysical properties. Using photobleaching infrared absorption, we determined quantum yields of photochemistry for nanosecond pulsed excitation at 355 and 532 nm. Changes in mass spectrometry during laser irradiation in vacuum measured the evolution of gaseous products. Fluorescence spectra, quantum yields, and lifetimes were measured to observe radiative channels of energy decay that compete with photochemistry. For the 6 materials studied, quantum yields of photochemistry ranged from <10 –5 to 0.03 and quantum yield of fluorescence ranged from <10 –3 to 0.33. In all cases, the photoexcitation nonradiatively relaxed primarily to heat, appropriate for supporting photothermal initiation processes. Lastly, the photochemistry observed was dominated by ring scission of the tetrazine, but there was evidence of more extensive multistep reactions as well.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Fine Tuning the CJ Detonation Speed of a High Explosive products Equation of State

For high explosive (HE) simulations, inaccuracies of a per cent or two in the detonation wave speed can result from not suficiently resolving the reaction zone width or from small inaccuracies in calibrating the products equation of state (EOS) or from variation of HE lots. More accurate detonation speeds can be obtained by ne tuning the equation of state to compensate. Here we show that two simple EOS transformations can be used to adjust the CJ detonation speed by a couple of per cent with minimal effect on the CJ release isentrope. The two transformations are (1) a shift in the energy origin and (2) a linear scaling of the speci c volume. The effectiveness of the transformations is demonstrated with simulations of the cylinder test for PBX 9502 starting with a products EOS for which the CJ detonation speed is 1 per cent too low.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2019

Measurements of the Dielectric Properties of Thin High-Explosive Samples Using a Parallel Plate Test Fixture

This report presents results of a study of the dielectric properties of several high explosive materials, including Composition B, C-4, Detasheet, Semtex 1A, Semtex 1H, and Semtex 10. The capacitance and dispersion of samples up to ten mm thick were measured at 24 and 65°C using a parallel plate test fixture. In this configuration, capacitance is proportional to the real component of the complex dielectric constant (or permittivity) of the material, while the dispersion is equal to the imaginary component of the dielectric constant divided by the real component. Measurements were performed at two temperatures to determine whether these dielectric properties might be used to monitor moderate temperature changes within these materials using an external fringing field capacitor. It was found that the real dielectric constant of the high explosives generally changed by only about 1% on heating from 24 to 65°C, and that the externally measured capacitance is therefore not a reliable parameter for monitoring temperature changes in these explosives. Temperature- based changes in the dispersion were often 20% or greater, and for several materials (e.g., Composition B, Detasheet) the temperature and dispersion showed good correlation as the temperature of the explosive was cycled up and down. It is thus possible that for some high explosives the externally measured dispersion is a useful parameter for monitoring temperature changes. However, other factors may limit the usefulness of this technique, including the need to have the plates of a fringing field capacitor in direct contact with the high explosive to obtain measurements, and the limited penetration depth of the fringing field into the explosive material.

36 MATERIALS SCIENCE↗
DOE OSTI2016

The escape of high explosive products: An exact-solution problem for verification of hydrodynamics codes

This paper documents the escape of high explosive (HE) products problem. The problem, first presented by Fickett & Rivard, tests the implementation and numerical behavior of a high explosive detonation and energy release model and its interaction with an associated compressible hydrodynamics simulation code. The problem simulates the detonation of a finite-length, one-dimensional piece of HE that is driven by a piston from one end and adjacent to a void at the other end. The HE equation of state is modeled as a polytropic ideal gas. The HE detonation is assumed to be instantaneous with an infinitesimal reaction zone. Via judicious selection of the material specific heat ratio, the problem has an exact solution with linear characteristics, enabling a straightforward calculation of the physical variables as a function of time and space. Lastly, implementation of the exact solution in the Python code ExactPack is discussed, as are verification cases for the exact solution code.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

The Trinity High Explosive Implosion System: The Foundation for Precision Explosive Applications

This article is set during the 1944 and 1945 final push to complete Project Y—the Manhattan Project at Los Alamos—and focuses primarily on overcoming the challenge of creating and demonstrating a successful convergent explosive implosion to turn a subcritical quantity of plutonium into a critical mass. The critical mass would then efficiently yield kilotons of trinitrotoluene (TNT)-equivalent energy in about a microsecond, demonstrating the implosion atomic bomb concept. This work culminated in the Trinity atomic test near Alamogordo on July 16, 1945. This implosion effect demarcated the approach to explosive science and technology the Laboratory has followed ever since, including development of high-explosive synthesis and formulation, small and large test and diagnostic facilities, shock dynamics theory, high-explosive system design engineering, and three-dimensional implosion modeling and simulation using some of the fastest computers in the world. This work also ushered in a period of broader application of precision high explosives in conventional munitions, demolition, mining and oil exploration, and space travel.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2017

Characterization of detonation soot produced during steady and overdriven conditions for three high explosive formulations

The detonation of high explosives (HE) produces a dense fluid of molecular gases and solid carbon. The solid detonation carbon contains various carbon allotropes such as detonation nanodiamonds, onion-like carbon, graphite and amorphous carbon, with the formation of the different forms dependent upon pressure, temperature and the environmental conditions of the detonation. We have collected solid carbon residues from controlled detonations of three HE formulations (Composition B-3, PBX 9501, and PBX 9502). Soot was collected from experiments designed to produce both steady and overdriven conditions, and from detonations in both an ambient (air) atmosphere and in an inert Ar atmosphere. Differences in solid carbon residues were quantified using X-ray photoelectron spectroscopy and carbon isotope measurements. Environmental conditions, HE formulation, and peak pressures influenced the amount of and isotopic composition of the carbon in the soot. Detonations in an Ar atmosphere produced greater amounts of carbon soot with lower δ 13 C values than those in ambient air. Therefore, solid carbon residues continued to evolve after detonation due to excess oxygen in the ambient air detonations. As well, higher peak pressures in overdriven conditions produced less carbon soot with, in general, higher δ 13 C values. Consequently, while overdriven conditions only produced peak pressures for a limited duration, it was enough to influence the composition of the solid carbon residues.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Metallurgical Failure Analysis of A2 Tool Steel Die Set from High Explosive Pellet Pressing Event

On 2 April 2018, a high explosive violent reaction (HEVR) occurred during routine pressing of a 1-in -diameter cylindrical pellet of PBX 9501 high explosive. Fragments of the die set (die body and stemples) involved in the event were sent to Sigma Division for metallurgical analysis. A handheld x-ray fluorescence alloy tester confirmed the die set material to be A2 tool steel. Light optical microscopy revealed what appear to be pre-existing flaws on the inner diameter of the die body. Scanning Electron Microscopy could neither confirm nor exclude the presence of fatigue cracking in the vicinity of these potential flaws. Energy Dispersive Spectroscopy indicated the presence of a carbon-bearing residue on fracture surfaces; nitrogen-bearing residue was also found. Optical microscopy revealed that the microstructure of the stemple and inner diameter of the die body contained large stringers and non-uniform grain size; this was distinct from the relatively clean and uniform microstructure seen at the outer diameter of the die body, and also other A2 tool steel stock (pedigree unknown and with no known connection to any HE pressing hardware) that was examined for additional comparison. Rockwell hardness testing indicated the material was heat treated properly. Metallographic analysis alone could not positively identify the root cause of the event, but, coupled with accounts provided by the operator and the successful history with the particular lot of HE involved in the event, points to ward mechanical failure of the die set due to pre -existing flaw as the most likely precipitating event. Suggestions for additional analyses and future qualification techniques are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2025

An In Situ , Automated High-Explosives Aging Method Utilizing Two-Dimensional Gas Chromatography–Mass Spectrometry

Understanding chemical changes that occur in high explosives as they age is of great importance to the safe employment and storage of these compounds. Traditional methods of aging high explosives even under accelerated aging conditions are time intensive with durations on the order of months to years. The nature of traditional aging analyses reduces each sample to a snapshot data point often separated widely in time, requiring many assumptions as to how the degradation products develop. Further complicating matters, several analytical techniques are typically employed for each sample analysis in order to ascertain an entire picture of the decomposition pathways. To address these shortcomings with existing methods, a new method of accelerated aging of high explosives utilizing comprehensive two-dimensional gas chromatography coupled to high-resolution mass spectrometry (GC × GC-HRMS) was developed using 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) as a model compound for method development. This in situ automated method reduces the time scale of aging to a matter of hours using the inlet of the GC × GC as the aging vessel. GC × GC in combination with HRMS allowed for the collection of both evolved gases and other decomposition products produced during the entire aging process in real time with HRMS providing far greater certainty in identification of explosives aging products. Additionally, this method allowed for a higher throughput of samples with greatly simplified sample preparation. Chemometric analysis of the GC × GC-HRMS data set via the alteration analysis (ALA) enabled discovery of statistically significant chemical changes providing insight into the variation of decomposition pathways with varying aging temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Uncertainty quantification of material parameters in modeling coupled metal and high explosive experiments

Experiments involving the coupling of metal and high explosives (HE) are of notable defense-related interest, and we seek to refine the uncertainty quantification associated with models of such experiments. In particular, our focus is on how uncertainty related to the metal constitutive model challenges our ability to infer high explosive model parameters when analyzing focused science experiments. We consider three focused experiments involving an HE accelerating metal: small plate tests with tantalum/LX-14 and tantalum/LX-17 pairings as well as a tantalum/LX-17 cylinder test. For all three models, we perform sensitivity analysis to ascertain the influence of metal strength on the coupled experimental response. Moreover, we calibrate each model in a Bayesian setting and study the quantification of metal strength on the inference of the HE parameters. Based on our results, we offer guidance for future metal/HE experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Moderate Velocity Ball Impact of a Mock High-Explosive

Modeling of thermal and mechanical events in high-explosive materials is complicated by the composite nature of the material, which experiences viscoelastic and plastic deformations and sustains damage in the form of microcracks that can dominate its overall behavior. A mechanical event of interest is projectile interaction with the material, which leads to extreme local deformation and adiabatic heating, which can potentially lead to adverse outcomes in an energetic material. Simulations of such an event predicted large local temperature rises near the path of a spherical projectile, but these were experimentally unconfirmed and hence potentially non-physical. This work concerns the experimental verification of local temperatures both at the surface and in the wake of a spherical projectile penetrating a mock (unreactive) high-explosive at {approx}700 m/s. Fast response thermocouples were embedded radially in a mid-plane of a cylindrical target, which was bonded around the thermocouples with epoxy and recorded by an oscilloscope through a low-pass filter with a bandwidth of 500 Hz. A peak temperature rise of 70 K was measured both at the equator of the projectile and in its wake, in good agreement with the temperature predicted in the minimally distorted elements at those locations by a finite element model in ABAQUS employing the ViscoSCRAM constitutive model. Further work is needed to elucidate the extreme temperature rises in material undergoing crushing or fragmentation, which is difficult to predict with meshed finite element methods due to element distortion, and also challenging to quantify experimentally.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Arc Initiation of High Explosives (Final Report)

Arc initiaition of high explosives (HE) can occur when electrical breakdown takes place at an interface or through the bulk of the HE. It can occur in accidental scenarios involving electrostatic discharge (ESD), natural scenarios such as lightning, and engineered scenarios such as spark detonators. The unique combination of short time scale, extremely high temperature, and relatively low pressure results in an initiation regime for which there was no first-principles understanding. The continuing need to understand and improve the safety of HE initiation systems in industrial, conventional munitions, and nuclear explosives environments drives us to acquire such first-principles understanding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Shock compression response of an insensitive high explosive single crystal: 1,1-diamino-2,2-dinitroethene (FOX-7)

Insensitive high explosives (IHEs) – that do not compromise performance – are of immense interest as a safer alternative to conventional high explosives, such as pentaerythritol tetranitrate (PETN) and cyclotrimethylenetrinitramine (RDX). Despite the strong interest in using IHEs, shock compression experiments on IHE single crystals have not been reported. To address this need, plate impact experiments were conducted to measure wave profiles in 1,1-diamino-2,2-dinitroethene (FOX-7) single crystals – a representative IHE crystal – shocked to 21 GPa longitudinal stress. Particle velocity histories, measured using laser interferometry, show a clear two-wave structure (elastic-inelastic response) at modest stresses (<3.8 GPa). Wave profiles at higher stresses show a single (overdriven) wave. Measured shock velocities and wave profiles provide accurate Hugoniot data to 21 GPa. The measured wave profiles to 21 GPa show no sign of energy release due to chemical decomposition and constitute the first demonstration of an IHE single crystal insensitivity under plane shock compression. Numerical simulations using a phenomenological material model developed for FOX-7 showed good agreement with the measured wave profiles. The experimental results and continuum simulations presented here constitute a significant first step in gaining insight into the shock compression response of IHE single crystals.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Comparison Between Surf and Multi-Shock Forest Fire High Explosive Burn Models

PAGOSA1 has several different burn models used to model high explosive detonation. Two of these, Multi-Shock Forest Fire and Surf, are capable of modeling shock initiation. Accurately calculating shock initiation of a high explosive is important because it is a mechanism for detonation in many accident scenarios (i.e. fragment impact). Comparing the models to pop-plot data give confidence that the models are accurately calculating detonation or lack thereof. To compare the performance of these models, pop-plots2 were created from simulations where one two cm block of PBX 9502 collides with another block of PBX 9502.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Effect of thermal conditioning on the initiation threshold of secondary high‐explosives

While most performance metrics of high–explosive (HE) based devices like detonation velocity, detonation pressure, and energy output are expected to degrade over time, the evolution of initiation threshold appears less clear, with claims of both increasing and decreasing trends in threshold having been made in the literature. This work analyzes D–optimally designed sequential binary test data for a few thermally conditioned porous–powder and polymer–bonded HE initiator systems using a Bayesian likelihood method employing the probit regression model. Here we find that in most cases the initiation threshold decreases (i.e., sensitivity increases) upon accelerated thermal conditioning. However, such results are nuanced and influenced by factors like the contact area of initiating stimulus, HE characteristics like density and specific surface area, as well as possible thermally induced changes to other materials and interfaces involved.

36 MATERIALS SCIENCE↗
DOE OSTI2018

High Explosive Detonation–Confiner Interactions

The primary purpose of a detonation in a high explosive (HE) is to provide the energy to drive a surrounding confiner, typically for mining or munitions applications. The details of the interaction between an HE detonation and its confinement are essential to achieving the objectives of the explosive device. For the high pressures induced by detonation loading, both the solid HE and confiner materials will flow. The structure and speed of a propagating detonation, and ultimately the pressures generated in the reaction zone to drive the confiner, depend on the induced flow both within the confiner and along the HE–confiner material interface. The detonation–confiner interactions are heavily influenced by the material properties and, in some cases, the thickness of the confiner. This review discusses the use of oblique shock polar analysis as a means of characterizing the possible range of detonation–confiner interactions. Computations that reveal the fluid mechanics of HE detonation–confiner interactions for finite reaction-zone length detonations are discussed and compared with the polar analysis. Furthermore this includes cases of supersonic confiner flow; subsonic, shock-driven confiner flow; subsonic, but shockless confiner flow; and sonic flow at the intersection of the detonation shock and confiner material interface. We also summarize recent developments, including the effects of geometry and porous material confinement, on detonation–confiner interactions.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2025

Detonation Waves in High Explosives

A material at high temperature can react or decompose. For an energetic material, the reaction is exothermic and releases chemical energy that would further increase the temperature. Under some circumstances, when a reaction is triggered, such a reaction can propagate and the material rapidly releases a large amount of energy giving rise to an explosion. Examples of such materials are aerosols, suspensions of solid particles or liquid droplets in a gas; such as coal dust, grain dust and fuel-air explosions. Frequently, explosions are due to accidents. A spectacularly destructive example is the recent explosion of a large quantity of ammonium nitrate (thousands of tons) in Beirut, Lebanon (August 2020); see for example Beirut explosion. Ammonium nitrate is used as a fertilizer. It and the aerosols are not considered to be explosives due to the limited conditions for which an explosion can occur. An aerosol gets the oxidizer from the surrounding air. Burning requires diffusion of the oxidizer to the particle surface where the reaction occurs. A large density of small particles is required for a fast enough reaction to support an explosion. In contrast, an explosive is an energetic material with both fuel and oxidizer mixed on a molecular scale (either premixed gases or within molecules of a solid). This allows fast enough reactions over a wide range of conditions to support a self-propagating reactive wave known as a detonation wave. A detonation wave can be controlled and an explosive used for useful purposes such as in mining, construction, demolition, explosive welding, argon flash lamp, pulsed power using a magnetic flux generator [see also Goforth et al., 2015], jet cutter with shaped charge, explosive art, and generating conditions to study the response of materials at high strain rates and high pressures [see for example, Marsh, 1980]. Explosives are also used in conventional munitions and nuclear weapons. The focus of this book is on the theory and phenomenology of solid high explosives (HEs); in particular, plastic-bonded explosives (PBXs). Some aspects of detonation wave theory are needed to interpret explosive data. Hence, the theory is presented before the detonation wave phenomenology. A familiarity with fluid flow, specifically the notion of shock waves and the shock loci are assumed. In the remainder of this chapter we give a brief overview on the basic properties of detonation waves and PBXs.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Investigating the electronic structure of high explosives with X-ray Raman spectroscopy

Abstract We investigate the sensitivity and potential of a synergistic experiment-theory X-ray Raman spectroscopy (XRS) methodology on revealing and following the static and dynamic electronic structure of high explosive molecular materials. We show that advanced ab-initio theoretical calculations accounting for the core-hole effect based on the Bethe-Salpeter Equation (BSE) approximation are critical for accurately predicting the shape and the energy position of the spectral features of C and N core-level spectra. Moreover, the incident X-ray dose typical XRS experiments require can induce, in certain unstable structures, a prominent radiation damage at room temperature. Upon developing a compatible cryostat module for enabling cryogenic temperatures ( $$\approx$$ ≈ 10 K) we suppress the radiation damage and enable the acquisition of reliable experimental spectra in excellent agreement with the theory. Overall, we demonstrate the high sensitivity of the recently available state-of-the-art X-ray Raman spectroscopy capabilities in characterizing the electronic structure of high explosives. At the same time, the high accuracy of the theoretical approach may enable reliable identification of intermediate structures upon rapid chemical decomposition during detonation. Considering the increasing availability of X-ray free-electron lasers, such a combined experiment-theory approach paves the way for time-resolved dynamic studies of high explosives under detonation conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

High Explosive Ignition through Chemically Activated Nanoscale Shear Bands

Shock initiation and detonation of high explosives is considered to be controlled through hot spots, which are local regions of elevated temperature that accelerate chemical reactions. Using classical molecular dynamics, we predict the formation of nanoscale shear bands through plastic failure in shocked TATB high explosive crystal. By scale-bridging with quantum-based molecular dynamics, we show that shear bands exhibit lower reaction barriers. While shear bands quickly cool,they remain chemically activated and support increased reaction rates without the local heating typically evoked by the hot spot paradigm. We describe this phenomenon as chemical activation through shear banding

Chemistry - Inorganic↗