Publications

Determination of product species, equations-of-state (EOS) and thermochemical properties of high explosives and pyrotechnics remains a major unsolved problem. Although, empirical EOS models may be calibrated to replicate detonation conditions within experimental variability (5--10%), different states, e.g. expansion, may produce significant discrepancy with data if the basic form of the EOS model is incorrect. A more physically realistic EOS model based on intermolecular potentials, such as the Jacobs Cowperthwaite Zwisler (JCZ3) EOS, is needed to predict detonation states as well as expanded states. Predictive capability for any EOS requires a large species data base composed of a wide variety of elements. Unfortunately, only 20 species have known JCZ3 molecular force constants. Of these 20 species, only 10 have been adequately compared to experimental data such as molecular scattering or shock Hugoniot data. Since data in the strongly repulsive region of the molecular potential is limited, alternative methods must be found to deduce force constants for a larger number of species. The objective of the present study is to determine JCZ3 product species force constants by using a corresponding states theory. Intermolecular potential parameters were obtained for a variety of gas species using a simple corresponding states technique with critical volume and critical temperature. A more complex, four parameter corresponding state method with shape and polarity corrections was also used to obtain intermolecular potential parameters. Both corresponding state methods were used to predict shock Hugoniot data obtained from pure liquids. The simple corresponding state method is shown to give adequate agreement with shock Hugoniot data.

A summary of multidimensional modeling is presented which describes coupled thermals chemical and mechanical response of reactive and nonreactive materials. This modeling addresses cookoff of energetic material (EM) prior to the onset of ignition. Cookoff, lasting from seconds to days, sensitizes the EM whereupon combustion of confined, degraded material determines the level of violence. Such processes are dynamic, occurring over time scales of millisecond to microsecond, and thus more amenable for shock physics analysis. This work provides preignition state estimates such as the amount of decomposition, morphological changes, and quasistatic stress states for subsequent dynamic analysis. To demonstrate a fully-coupled thermal/chemical/quasistatic mechanical capability, several example simulations have been performed: (1) the one-dimensional time-to-explosion experiments, (2) the Naval Air Weapon Center`s (NAWC) small scale cookoff bomb, (3) a small hot cell experiment and (4) a rigid, highly porous, closed-cell polyurethane foam. Predictions compared adequately to available data. Deficiencies in the model and future directions are discussed.

Cookoff modeling of confined energetic materials involves the coupling of thermal, chemical and mechanical effects. In the past, modeling has focussed on the prediction of thermal runaway with little regard to the effects of mechanical behavior of the energetic material. To address the mechanical response of the energetic material, a constitutive submodel has been developed which can be incorporated into thermal-chemical-mechanical analysis. This work presents development of this submodel and its incorporation into a fully coupled one-dimensional, thermal-chemical-mechanical computer code to simulate thermal initiation of energetic materials. Model predictions include temperature, chemical species, stress, strain, solid/gas pressure, solid/gas density, yield function, and gas volume fraction. Sample results from a scaled aluminum tube filled with RDX exposed to a constant temperature bath at 500 K will be displayed. The micromechanical submodel is based on bubble mechanics which describes nucleation, decomposition, and elastic/plastic mechanical behavior. This constitutive material description requires input of temperatures and reacted fraction of the energetic material as provided by the reactive heat flow code, XCHEM, and the mechanical response is predicted using a quasistatic mechanics code, SANTOS. A parametric sensitivity analysis indicates that a small degree of decomposition causes significant pressurization of the energetic material, which implies that cookoff modeling must consider the strong interaction between thermal-chemistry and mechanics. This document consists of view graphs from the poster session.

An eXplosive CHEMical kinetics code, XCHEM was developed to solve the reactive diffusion equations associated with thermal ignition of energetic material. This method-of-lines code uses stiff numerical methods and adaptive meshing. Solution accuracy is maintained between multilayered materials consisting of blends of reactive components and/or inert materials. Phase change and variable properties are included in one-dimensional slab, cylindrical and spherical geometries. Temperature-dependent thermal properties was incorporated and modification of thermal conductivities to include decomposition effects are estimated using solid/gas volume fractions determined by species fractions. Gas transport properties are also included. Time varying temperature, heat flux, convective and thermal radiation boundary conditions, and layer to layer contact resistances are also implemented. The global kinetic mechanism developed at Lawrence Livermore National Laboratory (LLNL) by McGuire and Tarver used to fit One-Dimensional Time to eXplosion (ODTX) data for the conventional energetic materials (HMX, RDX, TNT, and TATB) are presented as sample calculations representative of multistep chemistry. Calculated and measured ignition times for explosive mixtures of Comp B (RDX/TNT), Octol, (HMX/TNT), PBX 9404 (HMX/NC), and RX-26-AF (HMX/TATB) are compared. Geometry and size effects are accurately modeled, and calculations are compared to experiments with time varying boundary conditions. Finally, XCHEM calculations of initiation of an AN/oil/water emulsion, resistively heated, are compared to measurements.

The Becker-Kistiakowsky-Wilson equation of state (BKW-EOS) has been calibrated over a wide initial density range near C-J states using measured detonation properties from 62 explosives at III total initial densities. Values for the empirical BKW constants {alpha}, {beta}, {kappa}, and {theta} were 0.5, 0.298, 10.5, and 6620, respectively. Covolumes were assumed to be invariant. Model evaluation includes comparison to measurements from 91 explosives composed of combinations of Al, B, Ba, C, Ca, Cl, F, H, N, 0, P, Pb, and Si at 147 total initial densities. Adequate agreement between predictions and measurements were obtained with a few exceptions for nonideal explosives. However, detonation properties for the nonideal explosives can be predicted adequately by assuming partial equilibrium. The partial equilibrium assumption was applied to aluminized composites of RDX, HMX, TNETB, and TNT to predict detonation velocity and temperature.

Thermochemical data fits for approximately 900 gaseous and 600 condensed species found in the JANAF tables (Chase et al. 1985) have been completed for use with the TIGER non-ideal thermoequilibrium code (Cowperthwaite and Zwisler 1973). The TIGER code has been modified to allow systems containing up to 400 gaseous and 100 condensed constituents composed of up to 50 elements. Gaseous covolumes have been estimated following the procedure outlined by Mader (1979) using estimates of van der Waals radii for 48 elements and three-dimensional molecular mechanics. Molecular structures for all gaseous components were explicitly defined in terms of atomic coordinates in Å (Hobbs and Baer 1992a). The Becker-Kistiakowsky-Wilson equation of state (BKW-EOS) has been calibrated near C-J states using detonation temperatures measured in liquid and solid explosives and a large product species data base. Detonation temperatures for liquid and solid explosives were predicted adequately with a single set of BKW parameters. Values for the empirical BKW constants α, β, κ, and θ were 0.5, 0.174, 11.85, and 5160, respectively. Values for the covolume factors, κi, were assumed to be invariant. The liquid explosives included mixtures of hydrazine nitrate with hydrazine, hydrazine hydrate, and water; mixtures of tetranitromethane with nitromethane; liquid isomers ethylnitrate and 2-nitroethanol; and nitroglycerine. The solid explosives included HMX, RDX, PETN, Tetryl, and TNT. Color contour plots of HMX equilibrium products as well as thermodynamic variables are shown in pressure and temperature space. Similar plots for a pyrotechnic reaction composed of TiH2 and KClO4 are also reported. Calculations for a typical HMX-based propellant are also discussed. © 1992 Springer-Verlag.

Variations of bed void fraction in a full-scale, reacting, fixed-bed coal gasifier have been deduced from measured axial pressure profiles obtained during gasification of seven coal types ranging from lignite to bituminous. Packed-bed pressure correlations were used to calculate the void fractions based on monotonic polynomial fits of measured pressure profiles. Insights into the fixed-bed combustion processes affected by the void distribution were obtained by a one-dimensional, steady-state, fixed-bed combustion model. Predicted temperature profiles from this model compare reasonably well to experimental data. The bed void distributions are not linear but are perturbed by vigorous reactions in the devolatilization and oxidation zones. Results indicate that a dramatic increase in temperature and associated gas release causes the bed to expand and the gas void space to increase. Increased void space localized in the combustion zone causes the steep temperature gradient to decrease and the location of the maximum temperature to shift. Also, large feed gas flow rates cause the void fraction in the ash zone to increase.