Robert Knepper

Effect of varying bilayer spacing distribution on reaction heat and velocity in reactive Al/Ni multilayers

Self-propagating reactions in Al/Ni nanostructured multilayer foils are examined both experimentally and computationally to determine the impact of variations in reactant spacing on reaction properties. Heats of reaction and reaction velocities have been characterized as a function of average bilayer spacing for sputter-deposited, single-bilayer foils (having a uniform bilayer spacing) and for dual-bilayer foils (having two different bilayer spacings that are labeled thick and thin). In the latter case, the spatial distribution of the thick and thin bilayers is found to have a significant effect on reaction velocity, with coarse distributions leading to much higher reaction velocities than fine distributions. Numerical simulations of reaction velocity match experimental data well for most spatial distributions, with the exception of very coarse distributions or distributions containing very small bilayer spacings. A simple model based on thermal diffusivities and reaction velocities is proposed to predict when the spatial distribution of thick and thin bilayers becomes coarse enough to affect reaction velocity. This combination of experiment and simulation will allow for more effective design and prediction of reaction velocities in both sputter-deposited and mechanically processed reactive materials with variable reactant spacings.

Characterization of self-propagating formation reactions in Ni/Zr multilayered foils using reaction heats, velocities, and temperature-time profiles

We report on intermetallic formation reactions in vapor-deposited multilayered foils of Ni/Zr with 70 nm bilayers and overall atomic ratios of Ni:Zr, 2 Ni:Zr, and 7 Ni:2 Zr. The sequence of alloy phase formation and the stored energy is evaluated at slow heating rates (∼1 K/s) using differential scanning calorimetry traces to 725 °C. All three chemistries initially form a Ni–Zr amorphous phase which crystallizes first to the intermetallic NiZr. The heat of reaction to the final phase is 34–36 kJ/mol atom for all chemistries. Intermetallic formation reactions are also studied at rapid heating rates (greater than 105 K/s) in high temperature, self-propagating reactions which can be ignited in these foils by an electric spark. We find that reaction velocities and maximum reaction temperatures (Tmax) are largely independent of foil chemistry at 0.6±0.1 m/s and 1220±50 K, respectively, and that the measured Tmax is more than 200 K lower than predicted adiabatic temperatures (Tad). The difference between Tmax a...

Self-propagating reactions in Al/Zr multilayers: Anomalous dependence of reaction velocity on bilayer thickness

High temperature, self-propagating reactions are observed in vapor-deposited Al/Zr multilayered foils of overall atomic ratios 3 Al:1 Zr and 2 Al:1 Zr and nanoscale layer thicknesses; however, the reaction velocities do not exhibit the inverse dependence on bilayer thickness that is expected based on changes in the average diffusion distance. Instead, for bilayer thicknesses of 20-30 nm, the velocity is essentially constant at ∼7.7 m/s. We explore several possible explanations for this anomalous behavior, including microstructural factors, changes in the phase evolution, and phase transformations in the reactant layers, but find no conclusive explanations. We determine that the phase evolution during self-propagating reactions in foils with a 3 Al:1 Zr stoichiometry is a rapid transformation from Al/Zr multilayers to the equilibrium intermetallic Al3Zr compound with no intermediate crystalline phases. This phase evolution is the same for foils of 90 nm bilayer thicknesses and foils of bilayer thicknesses ...

Characterization of pore morphology in molecular crystal explosives by focused ion-beam nanotomography

The initiation and detonation properties of explosives are often empirically correlated to density, surface area, and particle size. Although these correlations are sometimes used successfully to predict the performance of bulk samples, the data are spatially averaged, which unfortunately muddles information critical to understanding fundamental processes. Density and surface area are essentially an indirect measure of porosity, which is arguably a more appropriate metric in many applications. We report the direct characterization of porosity in polycrystalline molecular crystal explosives by focused ion beam nanotomography, a technique that is typically reserved for robust materials such as ceramics and metals. The resulting three-dimensional microstructural data are incredibly rich, promising a substantial advance in our ability to unravel the processes governing initiation and detonation of molecular crystal explosives. In a larger context, this work demonstrates that focused ion beam nanotomography may be successfully extended to the investigation of nanoscale porosity in other molecular crystal or polymer materials.

Phase transformations, heat evolution, and atomic diffusion during slow heating of Al-rich Al/Zr multilayered foils

We describe the energy and sequence of phase transformations in multilayered Al/Zr foils with atomic ratios of 3 Al:1 Zr during low temperature (<350 °C) heat treatments in a differential scanning calorimeter. The initial phase formed is an Al-rich amorphous phase that appears to grow by Zr diffusion through the amorphous phase. The subsequent nucleation and growth of tetragonal Al3Zr along the Al/amorphous layer interface is mediated by Al diffusion through the crystalline intermetallic phase. Diffusion coefficients associated with these processes are higher than expected from reports of diffusivities measured at higher temperatures. The inferred heat of formation of the tetragonal Al3Zr phase is 1240 ± 40 J/g (53 ± 2 kJ/mol atom). No anomalous variation in the energy or sequence of phase transformations is found with bilayer thickness for samples with bilayer thickness in the range of 17 nm to 90 nm despite anomalies in the bilayer dependence of self-propagating reaction velocities in the same foils.

Controlling the shape of Al/Ni multilayer foils using variations in stress

Al/Ni multilayer foils were sputter-deposited with an in-plane residual stress state that was altered midway through the thickness of the foils by changing the bilayer spacing. The difference in stress between the top and bottom halves of the foil caused these systems to curl when they were removed from their substrates. As predicted, the radius of curvature increased linearly as the difference in stress between the upper and lower halves decreased and as foil thickness increased, demonstrating the ability to fabricate layered foils with specific curvatures. Unexpectedly, however, the radii of curvature of all the free-standing foils decreased with time after removal from their substrates, suggesting that a time-dependent relaxation mechanism was operating. An explanation based on stress driven, time-dependent deformation is offered to explain the relaxation, and an elasticity-based curvature model is presented for comparison with the measured steady state curvatures.

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

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.

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

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.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 4...

Near-Failure Detonation Behavior of Vapor-Deposited Hexanitrostilbene (HNS) films.

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.

Detonation corner turning in vapor-deposited explosives using the micromushroom test

Detonation corner turning describes the ability of a detonation wave to propagate into unreacted explosive that is not immediately in the path normal to the wave. The classic example of a corner tu...