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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Compressive strength of the plastic-bonded explosive surrogate idoxuridine under quasistatic and dynamic compression

Inert simulant materials, or “mocks”, are often used as surrogates for plastic-bonded explosives (PBX) in non-detonative tests in order to mitigate hazards. Mocks should reproduce as many non-detonative properties of the explosive as possible, including structural behavior in a variety of thermal and mechanical environments. Recently, the molecular crystal idoxuridine (IDOX) has been identified as an ideal mock for the main component in the explosive polymer-matrix composite PBX 9501, and has performed favorably under quasistatic loading conditions. Here, in order to assess robustness over a range of mechanical environments, plastic-bonded IDOX was compression tested from 0.001/s to 2000/s strain rates and compared to PBX 9501 historical data. Plastic-bonded IDOX showed good agreement to PBX 9501 across these strain rates, justifying continued development and production as a mock.

Burch, Alexandra C.↗
DOE OSTI2022

Lithium and boron isotopic compositions of olivine in chondrules from carbonaceous and ordinary chondrite meteorites: Implications for the origin of solar 11 B/ 10 B ratio

We report the origin of solar 11 B/ 10 B ratio ~4 remains an open question. It has been thought that a significant portion of boron in the Solar System was derived from continuous spallation nucleosynthesis during interactions between Galactic Cosmic Rays and C—N—O nuclei in the interstellar medium. However, because GCR-produced boron is characterized by 11 B/ 10 B ~2.5, an endmember with 11 B/ 10 B > 4 is required to account for the solar 11 B/ 10 B ratio. Two leading hypotheses for the sources of 11 B-rich components include low energy spallation in the Sun’s parental molecular cloud and the neutrino process during the supernova explosions. In this study, lithium and boron elemental and isotopic compositions of seven porphyritic olivine chondrules and one isolated olivine crystal from four meteorites (Allende, Yamato 81020, Asuka 12236, and QUE 97008) were determined in-situ to help constrain which of the two nucleosynthetic mechanisms has most likely supplied the forming Solar System with extra 11 B. Apparent isotopic variations in Li/Si, B/Si, δ 7 Li and δ 11 B were found in chondrule olivine crystals, but only three chondrules exhibit statistically resolved δ 11 B heterogeneities. Using these three chondrules as a basis for discussion, we evaluated the processes that could potentially cause elemental and isotopic variations of Li and B. We argue that the data can be best understood in the context of condensation of lithium-boron-rich material onto chondrule precursors in (an) initially heterogeneous gaseous reservoir(s), which could be realized if the Solar System derived 11 B-rich components from a supernova or supernovae.

58 GEOSCIENCES↗
DOE OSTI2023

Filming enhanced ionization in an ultrafast triatomic slingshot

Abstract Filming atomic motion within molecules is an active pursuit of molecular physics and quantum chemistry. A promising method is laser-induced Coulomb Explosion Imaging (CEI) where a laser pulse rapidly ionizes many electrons from a molecule, causing the remaining ions to undergo Coulomb repulsion. The ion momenta are used to reconstruct the molecular geometry which is tracked over time (i.e., filmed) by ionizing at an adjustable delay with respect to the start of interatomic motion. Results are distorted, however, by ultrafast motion during the ionizing pulse. We studied this effect in water and filmed the rapid “slingshot” motion that enhances ionization and distorts CEI results. Our investigation uncovered both the geometry and mechanism of the enhancement which may inform CEI experiments in many other polyatomic molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Intergranular Hotspots: A Molecular Dynamics Study on the Influence of Compressive and Shear Work

Numerous crystal- and microstructural-level mechanisms are at play in the formation of hotspots, which are known to govern high explosives initiation behavior. Most of these mechanisms, including pore collapse, interfacial friction, and shear banding, involve both compressive and shear work done within the material and have thus far remained difficult to separate. Here, we assess hotspots formed at shocked crystal–crystal interfaces using quasi-1D molecular dynamics simulations that isolate effects due to compression and shear. Two high explosive materials are considered (TATB and PETN) that exhibit distinctly different levels of molecular conformational flexibility and crystal packing anisotropy. Temperature and intramolecular strain energy localization in the hotspot are assessed through parametric variation of the crystal orientation and two velocity components that respectively modulate compression and shear work. The resulting hotspots are found to be highly localized to a region within 5–20 nm of the crystal–crystal interface. Compressive work plays a considerably larger role in localizing temperature and intramolecular strain energy for both materials and all crystal orientations considered. Shear induces a moderate increase in energy localization relative to unsheared cases only for relatively weak compressive shock pressures of approximately 10 GPa. These results help isolate and rank the relative importance of hotspot generation mechanisms and are anticipated to guide the treatment of crystal–crystal interfaces in coarse-grained models of polycrystalline high-explosive materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A Thermal and Nanomechanical Study of Molecular Crystals as Versatile Mocks for Pentaerythritol Tetranitrate

Pentaerythritol tetranitrate (PETN) is a commonly used high explosive (HE) in detonators. Often, surrogate or “mock” materials are used in place of HE for mechanical tests, proofing out equipment, or developing new diagnostics. However, there is no commonly accepted mock for PETN. A good mock should match at least one physical property of the target material, and ideally mimic multiple thermal and mechanical properties. Here, we investigate several molecular crystals to evaluate their efficacy in mocking PETN density, melting point, elastic modulus, hardness, plastic deformation, and fracture behavior. Materials were tested with a combination of calorimetry and nanoindentation. Two materials, 2,4,6-trifluorobenzoic acid (246 TFBA) and mesoerythritol, were downselected for detailed indentation study after the initial round of screening experiments, both were found to mimic PETN mechanical behavior quite well, 246 TFBA closer to PETN in most properties (hardness, modulus, and density) than erythritol, but erythritol having advantages in relative cost and matching the onset of yield. Depending on the desired implementation of the mock, one material may be preferred over the other, but both have potential as generic mocks for PETN. Nanoindentation is demonstrated as a versatile tool to provide rapid screening of these materials’ mechanical properties.

42 ENGINEERING↗
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 OSTI2025

Direct observation of ultrafast symmetry reduction during internal conversion of 2-thiouracil using Coulomb explosion imaging

The photochemistry of heterocyclic molecules plays a decisive role for processes and applications like DNA photo-protection from UV damage and organic photocatalysis. The photochemical reactivity of heterocycles is determined by the redistribution of photoenergy into electronic and nuclear degrees of freedom, initially involving ultrafast internal conversion. Most heterocycles are planar in their ground state and internal conversion requires symmetry breaking. To lower the symmetry, the molecule must undergo an out-of-plane motion, which has not yet been observed directly. Here we show using the example of 2-thiouracil, how Coulomb explosion imaging can be utilized to extract comprehensive information on this molecular deformation, linking the extracted deplanarization of the molecular geometry to the previously studied temporal evolution of its electronic properties. Particularly, the protons of the exploded molecule are well-suited messengers carrying rich information on its geometry at distinct times after electronic excitation. We expect that our new analysis approach centered on these peripheral protons can be adapted as a general concept for future time-resolved studies of complex molecules in the gas phase.

Chemical physics↗
DOE OSTI2025

Simultaneous imaging of vibrational, rotational, and electronic wave-packet dynamics in a triatomic molecule

Light-induced molecular dynamics often involve the excitation of several electronic, vibrational, and rotational states. Since the ensuing electronic and nuclear motion determines the pathways and outcomes of photoinduced reactions, our ability to monitor and understand these dynamics is crucial for molecular physics, physical chemistry, and photobiology. However, characterizing this complex motion represents a significant challenge when different degrees of freedom are strongly coupled. In this Letter, we demonstrate how the interplay between vibrational, rotational, and electronic degrees of freedom governs the evolution of molecular wave packets in the low-lying states of strong-field-ionized sulfur dioxide. Using time-resolved Coulomb explosion imaging (CEI) and quantum mechanical wave packet simulations, we directly map the bending vibrations of the molecule, show how the vibrational wave packet is influenced by molecular alignment, and elucidate the consequences of nuclear motion for the coupling between the two lowest electronic states of the cation. Furthermore, our results demonstrate that multicoincident CEI can be an efficient experimental tool for characterizing coupled electronic and nuclear motion in polyatomic molecules.

Atomic & molecular processes in external fields↗
DOE OSTI2022

Predicted Melt Curve and Liquid Shear Viscosity of RDX up to 30 GPa

Recent grain-scale simulations of HMX and TATB have shown that predictions for hot spot formation in high explosives are particularly sensitive to accurate determinations of the pressure-dependent melt curve and the shear viscosity of the liquid phase. These physics terms are poorly constrained beyond ambient pressure for the explosive RDX. Here we adopt an all-atom modeling approach using molecular dynamics (MD) simulations to predict the melt curve of RDX near to detonation conditions (30 GPa) and determine the shear viscosity of the liquid as a function of temperature and pressure above the melt curve. Phase-coexistence simulations were used to determine the melt curve, which is predicted to vary by almost 1100 K as the pressure increases from 0 GPa to 30 GPa. Equilibrium MD simulations and the Green-Kubo formalism were used to obtain the pressure-temperature-dependent shear viscosity. The shear viscosity of RDX is predicted to be of similar magnitude to the viscosity of TATB at low GPa-range pressures, and to be roughly an order of magnitude lower than the viscosity of HMX. The temperature dependence of the shear viscosity is Arrhenius at a given pressure, and the exponential pre-factor and activation term exhibit a strong, yet complicated, pressure dependence. An empirical pressure-temperature dependent function for RDX shear viscosity is developed that simultaneously captures a wide range of MD predictions while taking an analytic form that extrapolates smoothly beyond the fitted regime. The relative strength of the pressure and temperature dependencies of these two physics terms is found to be of similar magnitude for RDX, HMX, and TATB, which motivates incorporating these results in future RDX grain-scale modeling.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Bounding Pressure and Flammability Evaluations for a Department of Energy Standard Canister Loaded with Aluminum-Clad Spent Fuel

This report presents bounding pressurization and flammability evaluations from the radiolytic gas generation expected during extended (>50 years) dry storage of aluminum-clad spent nuclear fuel (ASNF) elements in a sealed Department of Energy (DOE) Standard Canister. The primary questions involving extended ASNF dry storage center around the adequacy of dry storage conditioning processes (i.e., drying) and the behavior of residual hydrated aluminum oxides on the cladding—specifically, the radiolytic breakdown of chemically bound water in these corrosion products. The objectives of the presented work include providing a bounding assessment of the pressure with respect to the DOE Standard Canister’s structural integrity limits and identifying the potential for forming flammable or explosive gas mixtures (i.e., exceedance of the lower flammability limit of the molecular hydrogen [H2] and oxygen [O2] concentrations). The evaluation results confirm the findings of previous, more complex M&S work. That is, the structural integrity of the canister remains unchallenged by a wide margin. Nevertheless, it is important to recognize that the presented pressure calculations consider a full breakdown of the chemisorbed water, including a consequent release of all available H2. In reality, the breakdown of water in these systems will likely remain incomplete, due to competing chemical and radiolytic reactions, thereby attaining an equilibrium in the storage environment.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Understanding Trigger Linkage Dynamics in Energetic Materials Using Mixed Picramide Nitrate Ester Explosives

The ability to predict the handling sensitivity of new organic energetic materials has been a longstanding goal. We report the synthesis and characterization of six new nitropicramide energetic materials with mixed functional groups that mimic known explosives such as nitroglycerin, erythritol tetranitrate (ETN), and pentaerythritol tetranitrate (PETN). The molecules have been studied theoretically using quantum molecular dynamics (QMD) simulations and density functional theory (DFT) calculations to identify the weakest bond in the reactants - the trigger-linkages - which control handling sensitivity, and to quantify their specific enthalpies of explosion. In good accord with the drop weight impact sensitivity data, our calculations predict that the sensitivities of the molecules are very similar owing to the small variations of the energy output and rates of trigger linkage rupture. In addition, both the QMD and DFT calculations point to the nitropicramide N–NO 2 bonds as the trigger linkages rather than the more typical O–NO 2 bonds. We propose that the switch of the trigger linkage from the nitrate esters to the nitramine groups arises from the strongly electron withdrawing character of the adjacent trinitrobenzene groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

X-ray induced Coulomb explosion imaging of transient excited-state structural rearrangements in CS2

Abstract Structural imaging of transient excited-state species is a key goal of molecular physics, promising to unveil rich information about the dynamics underpinning photochemical transformations. However, separating the electronic and nuclear contributions to the spectroscopic observables is challenging, and typically requires the application of high-level theory. Here, we employ site-selective ionisation via ultrashort soft X-ray pulses and time-resolved Coulomb explosion imaging to interrogate structural dynamics of the ultraviolet photochemistry of carbon disulfide. This prototypical system exhibits the complex motifs of polyatomic photochemistry, including strong non-adiabatic couplings, vibrational mode couplings, and intersystem crossing. Immediately following photoexcitation, we observe Coulomb explosion signatures of highly bent and stretched excited-state geometries involved in the photodissociation. Aided by a model to interpret such changes, we build a comprehensive picture of the photoinduced nuclear dynamics that follows initial bending and stretching motions, as the reaction proceeds towards photodissociation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

First principles reactive simulation for equation of state prediction

The high cost of density functional theory (DFT) has hitherto limited the ab initio prediction of the equation of state (EOS). In this article, we employ a combination of large scale computing, advanced simulation techniques, and smart data science strategies to provide an unprecedented ab initio performance analysis of the high explosive pentaerythritol tetranitrate (PETN). Comparison to both experiment and thermochemical predictions reveals important quantitative limitations of DFT for EOS prediction and thus the assessment of high explosives. In particular, we find that DFT predicts the energy of PETN detonation products to be systematically too high relative to the unreacted neat crystalline material, resulting in an underprediction of the detonation velocity, pressure, and temperature at the Chapman–Jouguet state. The energetic bias can be partially accounted for by high-level electronic structure calculations of the product molecules. Furthermore we demonstrate a modeling strategy for mapping chemical composition across a wide parameter space with limited numerical data, the results of which suggest additional molecular species to consider in thermochemical modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Thermal conductivity tensor of β -1,3,5,7-tetranitro-1,3,5,7-tetrazoctane ( β -HMX) as a function of pressure and temperature

Here, we have used reverse non-equilibrium molecular dynamics (RNEMD) simulations to determine the full thermal conductivity tensor for the monoclinic high explosive crystal β-1,3,5,7-tetranitro-1,3,5,7-tetrazoctane (β-HMX). In order to do so for the monoclinic crystal, four directions for heat propagation are used. Effects of the temperature and pressure are investigated between 200 and 500 K and 0 and 5 GPa, respectively, which approximately covers the range where the β polymorph is stable. Simulations are carried out with the Smith–Bharadwaj non-reactive empirical potential [Smith and Bharadwaj, J. Phys. Chem. B 103, 3570 (1999)], which is known to reproduce well the thermo-elastic properties of HMX. Our results indicate that the thermal conductivity, κ, is highly anisotropic, with 36% difference between the two extreme values at 300 K and 0 GPa. A simple function is used to interpolate κ in the pressure-temperature regime considered in this study, which can be used in continuum models. The results from RNEMD simulations compare well with available experimental results from the literature and allow the determination of κ for any direction and temperature and pressure within or around the fitting interval.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Prediction of impact sensitivity, heat of formation and heat of explosion using atomic connectivity

In these proceedings we revisit a large collection of explosives and explosive descriptors with the goal of predicting impact sensitivity using only local atomic environments that can be deciphered from molecular SMILES strings as descriptors without utilizing empirically measured values or computationally expensive electronic structure calculations. From the original database of nearly 500 descriptors, removing empirically measured and electronic structure values decreased the number of descriptors to 135, which we reduced to 18 the most important descriptors using Random Forests. The condensed model predicted impact sensitivity with essentially the same accuracy as the existing, more complex model (R 2 = 0.788 and RSME = 0.312), while remaining applicable to all types of explosives (Peroxides, azides, C-Nitros, Nitroamines, Nitrate Esters, etc.). In addition to impact sensitivity, we proposed similar models to accurately predict values heat of formation (ΔH f ) and heat of explosion (Q), with R 2 = 0.966 and 0.916, respectively. In conclusion, the work in these proceedings allows for prediction of explosive performance and sensitivity with only chemical structure information and an estimate of density.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Imaging transient molecular configurations in UV-excited diiodomethane

Femtosecond structural dynamics of diiodomethane (CH 2 I 2 ) triggered by ultraviolet (UV) photoabsorption at 290 and 330 nm are studied using time-resolved coincident Coulomb explosion imaging driven by a near-infrared probe pulse. Here, we map the dominant single-photon process, the cleavage of the carbon–iodine bond producing rotationally excited CH 2 I radical, identify the contributions of the three-body (CH 2 + I + I) dissociation and molecular iodine formation channels, which are primarily driven by the absorption of more than one UV photon, and demonstrate the existence of a weak reaction pathway involving the formation of short-lived transient species resembling iso-CH 2 I 2 -like geometries with a slightly shorter I–I separation compared to the ground-state CH 2 I 2 . These transient molecular configurations, which can be separated from the other channels by applying a set of conditions on the correlated momenta of three ionic fragments, are formed within ∼100 fs after the initial photoexcitation and decay within the next 100 fs.

Atomic and molecular processes↗