A numerical model is developed to study the shock wave ignition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystal. The model accounts for the coupling between crystal thermal/mechanical responses and chemical reactions that are driven by the temperature field. This allows for the direct numerical simulation of decomposition reactions in the hot spots formed by mechanical loading. The model is used to simulate intragranular pore collapse under shock wave loading. In a reference case: (i) shear-enabled micro-jetting is responsible for a modest extent of reaction in the pore collapse region, and (ii) shear banding is found to be an important mode of localization. The shear bands, which are filled with molten HMX, grow out of the pore collapse region and serve as potential ignition sites. The model predictions of shear banding and reactivity are found to be quite sensitive to the respective flow strengths of the solid and liquid phases. In this regard, it is shown that reasonable assumptions of liquid-HMX viscosity can lead to chemical reactions within the shear bands on a nanosecond time scale.

Direct numerical simulation of shear localization and decomposition reactions in shock-loaded HMX crystal

Anion exchange membrane fuel cells (AEMFCs) have attracted extensive attention in the recent years, primarily due to the distinct advantage potentials they have over the mainstream proton exchange membrane fuel cells. The anion exchange membrane (AEM) is the key component of AEMFC systems. Because of the unique characteristics of water management in AEMFCs, understanding the water mobility through AEMs is key for this technology, as it significantly affects (and limits) overall cell performances. This work presents a study of the equilibrium state and kinetics of water uptake (WU) for AEMs exposed to vapor source H2O. We investigate different AEMs that exhibit diverse water uptake behaviors. AEMs containing different backbones (fluorinated and hydrocarbon-based backbones) and different functional groups (various cations as part of the backbone or as pendant groups) were studied. Equilibrium WU isotherms are measured and fitted by the Park model. The influence of relative humidity and temperature is also s...

Water Uptake Study of Anion Exchange Membranes

The shock and detonation response of high explosives has been an active research topic for more than a century. In recent years, high quality data from experiments using embedded gauges and other diagnostic techniques have inspired the development of a range of new high-fidelity computer models for explosives. The experiments and models have led to new insights, both at the continuum scale applicable to most shock and detonation experiments, and at the mesoscale relevant to hotspots and burning within explosive microstructures. This article reviews the continuum and mesoscale models, and their application to explosive phenomena, gaining insights to aid future model development and improved understanding of the physics of shock initiation and detonation propagation. In particular, it is argued that “desensitization” and the effect of porosity on high explosives can both be explained by the combined effect of thermodynamics and hydrodynamics, rather than the traditional hotspot-based explanations linked to ...

Understanding the shock and detonation response of high explosives at the continuum and meso scales

Mussel-inspired coating of energetic crystals: A compact core–shell structure with highly enhanced thermal stability

A computational strategy based on coupling density functional theory, variational transition state theory, and a microscale materials morphology description unravels details of the defect-induced effect on the surface decomposition of molecular crystals. The technique allows us to resolve the earliest stages of decomposing solids, even for very complex materials and for ultrafast chemical reactions. A comparative analysis of chemical decomposition reactions in HMX with progressively increasing system complexity (an isolated HMX molecule; a perfect single HMX crystal; a defect-containing, porous, and granular HMX crystal) demonstrates that the initiation of the material's degradation can be effectively manipulated by changing the crystal morphology. The activation barriers, reaction constants, and corresponding reaction rates are obtained as a function of molecular environment (a molecule in a vacuum, in an ideal bulk crystal, on a surface or interface, and on a defect in a solid), and decomposition times are predicted. The computational approach can be applied to any other material and system.

Rapid materials degradation induced by surfaces and voids: ab initio modeling of β-octatetramethylene [corrected] tetranitramine.

The dynamic and equilibrium water vapor sorption properties of Sylgard-184, a commercially available poly(dimethylsiloxane) elastomer (PDMS), were determined via gravimetric analysis from 30 to 70 °C. Described here is a methodology for quantitatively assessing how water vapor diffuses and ad/absorbs into polymeric materials that are traditionally considered hydrophobic. PDMS materials are frequently chosen for their moisture barrier properties; our results, however, demonstrate that moisture is able to penetrate the material over a range of temperatures and humidities. The sorption values measured here ranged from ca. 0.1 to 1.4 cm3 (STP) H2O/g Sylgard. The isotherms exhibited sigmoidal character and were fit to a triple mode sorption model. Asymptotic behavior at low water activities was characterized using a Langmuir type adsorption model, linear behavior was fit to a Henry’s law type dependence, and the convex portion at higher activities was fit with good agreement to Park’s equation for pooling or c...

Thermodynamic study on dynamic water vapor sorption in Sylgard-184.

The effect of pressure on the global thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Global decomposition rates were determined by fitting the fraction reacted to the extended-Prout−Tompkins nucleation−growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low-to-moderate pressures (i.e., between ambient pressure and 0.1 GPa) and decelerates the decomposition at higher pressures. The decomposition acceleration is attributed to pressure-enhanced autocatalysis, whereas the deceleration at high pressures is attributed to pressure-inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both the β- and δ-polymorphs of HMX are...

Pressure-Dependent Decomposition Kinetics of the Energetic Material HMX up to 3.6 GPa

HMX-based explosives LX-10 and PBX-9501 were heated through the β-δ phase transition. Ultra-small angle x-ray scattering (USAXS) and molecular diffraction were simultaneously recorded as the HMX was heated. Mesoscale voids and structure dramatically change promptly with the β-δ phase transition, rather than with other thermal effects. Also, x-ray induced damage, observed in the USAXS, occurs more readily at elevated temperatures; as such, the dose was reduced to mitigate this effect. Optical microscopy performed during a similar heating cycle gives an indication of changes on longer length scales, while x-ray microtomography, performed before and after heating, shows the character of extensive microstructural damage resulting from the temperature cycle and solid-state phase transition.

Mesoscale evolution of voids and microstructural changes in HMX-based explosives during heating through the β-δ phase transition

The time scale and/or products of photoinduced decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) were investigated at ambient pressure and compared with products formed at 8 GPa. Ultrafast time-resolved infrared and steady-state Fourier transform IR (FTIR) spectroscopies were used to probe TATB and its products after photoexcitation with a 5 ns pulse of 532 nm light. At ambient pressure, transient spectra of TATB indicate that the molecule has significantly decomposed within 60 ns; transient spectra also indicate that formation of CO2, an observed decomposition product, is complete within 30−40 μs. Proof of principle time-resolved experiments at elevated pressures were performed and are discussed briefly. Comparison of steady-state FTIR spectra obtained at ambient and elevated pressure (ca. 8 GPa) indicate that the decomposition products vary with pressure. We find evidence for water as a decomposition product only at elevated pressure.

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Elizabeth A. Glascoe

Papers

Thermodynamic study on dynamic water vapor sorption in Sylgard-184.

Pressure-Dependent Decomposition Kinetics of the Energetic Material HMX up to 3.6 GPa

Mesoscale evolution of voids and microstructural changes in HMX-based explosives during heating through the β-δ phase transition

Nanosecond Time-Resolved and Steady-State Infrared Studies of Photoinduced Decomposition of TATB at Ambient and Elevated Pressure

The response of the HMX-based material PBXN-9 to thermal insults: Thermal decomposition kinetics and morphological changes