Exploding bridgewire (EBW) detonators are used to rapidly and reliably initiate energetic reactions by exploding a bridgewire via Joule heating. While the mechanisms of EBW detonators have been studied extensively in nominal conditions, comparatively few studies have addressed thermally damaged detonator operability. We present a mesoscale simulation study of thermal damage in a representative EBW detonator, using discrete element method (DEM) simulations that explicitly account for individual particles in the pressed explosive powder. We use a simplified model of melting, where solid spherical particles undergo uniform shrinking, and fluid dynamics are ignored. The subsequent settling of particles results in the formation of a gap between the solid powder and the bridgewire, which we study under different conditions. In particular, particle cohesion has a significant effect on gap formation and settling behavior, where sufficiently high cohesion leads to coalescence of particles into a free-standing pellet. This behavior is qualitatively compared to experimental visualization data, and simulations are shown to capture several key changes in pellet shape. We derive a minimum and maximum limit on gap formation during melting using simple geometric arguments. In the absence of cohesion, results agree with the maximum gap size. With increasing cohesion, the gap size decreases, eventually saturating at the minimum limit. We present results for different combinations of interparticle cohesion and detonator orientations with respect to gravity, demonstrating the complex behavior of these systems and the potential for DEM simulations to capture a range of scenarios.
Determining the thermal response of energetic materials at high densities can be difficult when pressure dependent reactions occur within the interior of the material. At high temperatures, reactive components such as hexahydro-l,3,5-tri-nitro-l,3,5-triazine (RDX), ammonium perchlorate (AP), and hydroxyl-terminated polybutadiene (HTPB) decompose and interact. The decomposition products accumulate near defects where internal pressure ultimately causes mechanical damage with closed pores transitioning into open pores. Gases are no longer confined locally; instead, they freely migrate between open pores and ultimately escape into the surrounding headspace or vent. Recently we have developed a universal cookoff model (UCM) coupled to a micromechanics pressurization (MMP) model to address pressure-dependent reactions that occur within the interior of explosives. Parameters for the UCM/MMP model are presented for an explosive and two propellants that contain similar portions of both aluminum (Al) and a binder. The explosive contains RDX and the propellants contain AP with no RDX. One of the propellants contains small amounts of curing catalysts and a burn modifier whereas the other propellant does not. We found that the cookoff behavior of the two propellants behave similarly leading and conclude that small amounts of catalysts or burn modifiers do not influence cookoff behavior appreciably. Kinetic parameters for the UCM/MMP models were obtained from the Sandia Instrumented Thermal Ignition (SITI) experiment. Validation is done with data from other laboratories.
Large rocket motors may violently explode when exposed to accidental fires. Even hot metal fragments from a nearby accident may penetrate the propellant and ultimately cause thermal ignition. A mechanistic understanding of heated propellants leading to thermal runaway is a major unsolved problem. Here we show that thermal ignition in propellants can be predicted using a universal cookoff model coupled to a micromechanics pressurization model. Our model predicts the time to thermal ignition in cookoff experiments with variable headspace volumes. We found that experiments with headspace volumes are more prone to deformation which distorts pores and causes increased permeability when the propellant expands into this headspace. Delayed ignition with larger headspace volume correlates with lower headspace pressures during decomposition. We found that our predictions matched experimental measurements best when the initial propellant was impermeable to gas flow rather than being permeable. Similar behavior is expected with other energetic materials with rubbery binders. Our model is validated using data from a separate laboratory. We also present an uncertainty analysis using Latin Hypercube Sampling (LHS) of thermal ignition caused by a steel fragment embedded in the propellant.
Hobbs, Michael L.; Britt, Phillip F.; Hobbs, David T.; Kaneshige, Michael; Minette, Michael; Mintz, Jessica; Pennebaker, Frank M.; Parker, Gary R.; Rosenberg, David; Schwantes, Jon; Williams, Audrey; Pierce, Robert
Hobbs, Michael L.; Britt, Phillip F.; Hobbs, David T.; Kaneshige, Michael; Minette, Michael; Mintz, Jessica; Pennebaker, Frank M.; Parker, Gary R.; Pierce, Robert; Rosenberg, David; Schwantes, Jon; Williams, Audrey
Precise wording is important in every field of study, including operational procedures. Confusion in the wording “organic” and “inorganic” may have contributed to substitution of an organic kitty litter for an inorganic adsorbent used to prepare nuclear waste for disposal at an underground salt repository. Adsorbents prevent liquids like nitric acid from causing corrosion within the waste drums. However, combination of organic material with nitric acid can cause heat- and gas-generating reactions resulting in thermal runaway, rapid pressurization, and drum rupture. In 2014, waste Drum 68660 containing nitric acid-soaked organic kitty litter exploded and released transuranic waste into the repository. The cause of the accident was never identified. Here we show that the root cause of Drum 68660 igniting was restriction of the drum vent resulting in accelerated nitric acid chemistry, thermal runaway, and radiation dispersal.
Operability thresholds that differentiate between functional RP-87 exploding bridge wire (EBW) detonators and nonfunctional RP-87 EBW detonators (duds) were determined by measuring the time delay between initiation and early wall movement (function time). The detonators were inserted into an externally heated hollow cylinder of aluminum and fired with current flow from a charged capacitor using an exploding bridge wire (EBW initiated). Functioning detonators responded like unheated pristine detonators when the function time was 4 μs or less. The operability thresholds of the detonators were characterized with a simple decomposition cookoff model calibrated using a modified version of the Sandia Instrumented Thermal Ignition (SITI) experiment. These thresholds are based on the calculated state of the PETN when the detonators fire. The operability threshold is proportional to the positive temperature difference (ΔT) between the maximum temperature within the PETN and the onset of decomposition (∼406 K). The temperature difference alone was not sufficient to define the operability threshold. The operability threshold was also proportional to the time that the PETN had been at elevated temperatures. That is, failure was proportional to both temperature and reaction rate. The reacted gas fraction is used in the current work for the reaction correlation. Melting of PETN also had a significant effect on the operability threshold. Detonator failure occurred when the maximum temperature exceeded the nominal melting point of PETN (414 K) for 45±5 s or more.
Transforming polymorphs, melting, and boiling are physical processes that can accelerate decomposition rates during cookoff of PETN and make measurements difficult. For example, splashing liquids from large bubbles filled with decomposition products clog pressure tubing in sealed experiments. Boil over can also extinguish thermal excursions in vented experiments making ignition difficult. For better measurements, we have modified the Sandia Instrumented Thermal Ignition (SITI) experiment to obtain better sealed and vented cookoff data for PETN by reducing the sample size and including additional gas space to prevent clogged tubing and boil over. Ignition times were not affected by 1) increasing the gas space by a factor of 3 in sealed SITI experiments or by 2) venting the decomposition gasses. That is, thermal ignition of PETN is not pressure dependent and the rate-limiting step during PETN decomposition likely occurs in the condensed phase. A simple decomposition model was calibrated using these observations and includes rate acceleration caused by melting and boiling. The model is used to predict internal temperatures, pressurization, and thermal ignition in a wide variety of experiments. The model is also used with SITI data to estimate the previously unreported latent enthalpy (5 J/g) associated with the α (PETN-I) to β (PETN-II) polymorphic phase transformation of PETN.
Cookoff experiments of powdered and pressed TATB-based plastic bonded explosives (PBXs) have been modeled using a pressure-dependent universal cookoff model (UCM) in combination with a micromechanics pressurization (MMP) model described in a companion paper. The MMP model is based on the accumulation of decomposition gases at nucleation sites that load the surrounding TATB crystals and binder. This is the first cookoff model to use an analytical mechanics solution for compressibility and thermal expansion to describe internal pressurization caused by both temperature and decomposition occurring within closed-pore explosives. This approach produces more accurate predictions of ignition time and pressurization within high-density explosives than simple equation-of-state models. The current paper gives details of the reaction chemistry, model parameters, predicted uncertainty, and validation using experiments from multiple laboratories with errors less than 6 %. The UCM/MMP model framework gives more accurate thermal ignition predictions for high density explosives that are initially impermeable to decomposition gases.
We have completed a series of both vented and sealed cookoff experiments of black powder and smokeless powder in our Sandia Instrumented Thermal Ignition (SITI) apparatus at bulk densities of 1078 and 729 kg/m3, respectively. The confining aluminum cylinder was ramped from room temperature to a set point temperature and then held at the setpoint temperature until ignition. The setpoint temperatures varied between 495 to 523 K for the black powder and 401 to 412 K for the more sensitive smokeless powder. The vented experiments show a significant delay in thermal ignition, indicating that the ignition is dependent on pressure. Post experimental debris shows greater violence for our smokeless powder experiments than our black powder experiments. A simplified universal cookoff model (UCM) was calibrated using the black powder and smokeless powder SITI data and used to predict pressurization and thermal ignition. The current work presents the first calibration of the UCM with a double base propellant. This work also presents the first pressure-dependent cookoff model for black powder and smokeless powder.
We have completed a series of vented and sealed cookoff experiments of the ε-polymorph of CL-20 in our Sandia Instrumented Thermal Ignition (SITI) apparatus using both powder and pressed pellets at nominal densities of 313 ± 8 kg/m3 and 1030 ± 4 kg/m3, respectively. The boundary temperature of our aluminum confinement cylinder was ramped in 10 minutes from room temperature to a prescribed set-point temperature ranging between 448 nd 468 K and held at the set-point temperature until ignition. A universal cookoff model (UCM) has been calibrated using the ε-CL-20 SITI data to predict pressurization and thermal ignition of ε-CL-20. The ignition model was validated by using one-dimensional time-to-explosion (ODTX) ignition data from a different laboratory. We found that a thirtyfold increase in the reaction rates due to liquefaction at 520 K could explain the high temperature ODTX cookoff data. The model gives a plausible explanation of why melting is important in fast cookoff events involving CL-20. Our model also gives support to 520 K as the liquefaction point of CL-20, which has different values in the literature.
In the present study, commercially available detonators with pentaerythritol tetranitrate (PETN) were subjected to elevated temperatures. The detonators were thermally ignited over a range of heating rates to measure ignition delay time and assess detonator violence. The violence of the detonator was quantified by measuring the velocity of the detonator closure disc (or "flyer"). The maximum flyer velocity of a thermally ignited detonator was comparable in magnitude to that obtained by initiating a room temperature pristine detonator with an exploding bridge wire (under the same confinement); however, the high flyer velocity was not an indication of deflagration to detonation transition (DDT) in the thermally ignited detonator. The detonator responded more violently than a thermally ignited detonator when initiated at 95% of the ignition delay time. Inoperability thresholds were also measured by varying the detonator temperature and the threshold was found to be sensitive at detonator temperatures below the melting point of PETN.
The solubility of RDX (hexahydro-1,3,5-tri-nitro-1,3,5-triazine) in TNT (2,4,6-trinitrotoluene) at elevated temperatures is required to accurately predict the response of Comp-B3 (60:40 RDX:TNT) during accidents involving fire. As the temperature increases, the TNT component melts, the RDX partially dissolves in the liquid TNT, and the remaining RDX melts (203 ∘C) as the Comp-B thermally ignites. In the current work, we used a differential scanning calorimeter (DSC) to estimate the solubility of RDX in TNT at the melting point of RDX. Most DSC measurements of Comp-B3 do not show an RDX melt endotherm. The absence of an endotherm associated with the RDX melt has been interpreted as RDX being completely dissolved in TNT before reaching the melting point. We have observed that the endotherm is not absent, but is masked by exothermic reactions occurring at these elevated temperatures. We have inhibited the exothermic reactions by venting our DSC samples and measuring the RDX melt endotherm in our Comp-B3 samples at about 203 ∘C. Using the measured heat flow associated with the RDX melt and the latent melting enthalpy of RDX, we have approximated the solubility of RDX in TNT to be roughly 50–100 g RDX per 100 g TNT. The broad range is based on corrections for exothermic reactions occurring as the RDX melts.
On June 30, 2020, a 0.87 gram PETN charge being pressed in the Rapid Prototyping Facility (RPF), unexpectedly initiated, resulting in destruction of the pressing fixture but no injuries or facility damage. In response, the Safety Review Board (SRB) met on Aug. 13, 2020 and Oct. 1, 2020 to review information collected following the incident, consider likely direct causes, and form recommendations.
Thermal conductivity has been determined for a variety of energetic materials (EMs) using finite element analysis (FEA) and cookoff data from the Sandia Instrumented Thermal Ignition (SITI) experiment. Materials studied include melt-cast, pressed, and low-density explosives. The low-density explosives were either prills or powders with some experiments run at pour density (not pressed). We have compared several of our thermal conductivities with those in the literature as well as investigated contact resistance between the confining aluminum and explosive, multidimensional heat transfer effects, and uncertainty in the thermocouple bead positions. We have determined that contact resistance is minimal in the SITI experiment, the heat transfer along the midplane is one-dimensional, and that uncertainty in the thermocouple location is greatest near the heated boundary. Our values of thermal conductivity can be used with kinetic mechanisms to accurately predict thermal profiles and energy dissipation during the cookoff of explosives.
Validated models of melt cast explosives exposed to accidental fires are essential for safety analysis. In the current work, we provide several experiments that can be used to develop and validate cookoff models of melt cast explosives such as Comp-B3 composed of 60:40 wt% RDX:TNT. We present several vented and sealed experiments from 2.5 mg to 4.2 kg of Comp-B3 in several configurations. We measured pressure, spatial temperature, and ignition time. Some experiments included borescope images obtained during both vented and sealed decomposition. We observed the TNT melt, the suspension of RDX particles in the melt, bubble formation caused by RDX decomposition, and bubble-induced mixing of the suspension. The RDX suspension did not completely dissolve, even as temperatures approached ignition. Our results contrast with published measurements of RDX solubility in hot TNT that suggest RDX would be completely dissolved at these high temperatures. These different observations are attributed to sample purity. We did not observe significant movement of the two-phase mixture until decomposition gases formed bubbles. Bubble generation was inhibited in our sealed experiments and suppressed mixing.
We have completed a series of small-scale cook-off experiments of ammonium nitrate (AN) prills in our Sandia Instrumented Thermal Ignition test at nominal packing densities of about 0.8 g/cm3. We increased the boundary temperature of our aluminum confinement cylinder from room temperature to a prescribed set-point temperature in 10 min. Our set-point temperature ranged from 508 to 538 K. The external temperature of the confining cylinder was held at the set-point temperature until ignition. We used type K thermocouples to measure temperatures associated with several polymorphic phase changes as well as melting and boiling. As the AN boiled, our thermocouples were destroyed by corrosion, which may have been caused by reaction of hot nitric acid (HNO3) with nickel to form nickel nitrate, Ni(NO3)2. Videos of the corroding thermocouples showed a green solution that was similar to the color of Ni(NO3)2. We found that ignition was imminent as the AN boiling point was exceeded. Ignition of the AN prills was modeled by solving the energy equation with an energy source due to desorption of moisture and decomposition of AN to form equilibrium products. A Boussinesq approximation was used in conjunction with the momentum equation to model flow of the liquid AN. We found that the prediction of ignition was not sensitive to small perturbations in the latent enthalpies.
We have used several configurations of the Sandia Instrumented Thermal Ignition (SITI) experiment to develop a pressure-dependent, four-step ignition model for a plastic bonded explosive (PBX 9407) consisting of 94 wt.% RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and a 6 wt.% VCTFE binder (vinyl chloride/chlorotrifluoroethylene copolymer). The four steps include desorption of water, decomposition of RDX to form equilibrium products, pressure-dependent decomposition of RDX forming equilibrium products, and decomposition of the binder to form hydrogen chloride and a nonvolatile residue (NVR). We address drying, binder decomposition, and decomposition of the RDX component from the pristine state through the melt and into ignition. We used Latin Hypercube Sampling (LHS) of the parameters to determine the sensitivity of the model to variation in the parameters. We also successfully validated the model using one-dimensional time-to-explosion (ODTX and P-ODTX) data from a different laboratory. Our SITI test matrix included 1) different densities ranging from 0.7 to 1.63 g/cm3, 2) free gas volumes ranging from 1.2 to 38 cm3, and 3) boundary temperatures ranging from 170 to 190 °C. We measured internal temperatures using embedded thermocouples at various radial locations as well as pressure using tubing that was connected from the free gas volume (ullage) to a pressure gauge. We also measured gas flow from our vented experiments. A borescope was included to obtain in situ video during some SITI experiments. We observed significant changes in the explosive volume prior to ignition. Our model, in conjunction with data observations, imply that internal accumulation of decomposition gases in high density PBX 9407 (90% of the theoretical maximum density) can contribute to significant strain whether or not the experiment is vented or sealed.
In previous studies, we found that the nitroplasticizer in the HMX-based explosive PBX 9501 played a crucial role in cookoff, especially when predicting response in larger systems. We have recently completed experiments with a similar explosive, LX-14, that has a relatively nonreactive binder. We expected the ignition times for LX-14 to be longer than PBX 9501 since PBX 9501 has a more reactive binder. However, our experiments show the opposite trend. This paradox can be explained by retention of reactive gases within the interior of LX-14 by the higher strength binder resulting in faster ignition times. In contrast, the binder in PBX 9501 melts at low temperatures and does not retain decomposition gases as well as the LX- 14 binder. Retention of reactive gases in LX-14 may also explain the more violent response in oblique impact tests when compared to PBX 9501.
Kaneshige, Michael; Rabbi, Md F.; Mach, Robert; Catzin, Carlos A.; Stewart, Calvin M.
Simulant polymer bonded explosives are widely used to simulate the mechanical response of real energetic materials. In this paper, the fracture resistance of a simulant polymer bo nded explosive (PBX) is experimentally investigated. The simulant is composed of 80 wt.% soda lime glass beads (SLGB) and 20 wt.% high impact Polystyrene 825 (HIPS). Brazilian disk tests are performed to characterize the tensile and compressive properties. Fracture toughness and energy tests are performed in the semi - circular bending (SCB) configuration on 80, 81, 82, and 83 wt % SLGB compositions. Digital image correlation is performed to record the surface displacements and calculate surface strains during testing. The m icromechanical behavior of ductile and brittle fracture are evaluated using digital microscopy and scanning electron microscopy of the fracture surface. It is determined that (i) the manufacturing process produces a credible simulant of PBX properties, and (ii) the SCB test measures fracture resistance with a reasonable coefficient of variation.
In this study, we have made reasonable cookoff predictions of large-scale explosive systems by using pressure-dependent kinetics determined from small-scale experiments. Scale-up is determined by properly accounting for pressure generated from gaseous decomposition products and the volume that these reactive gases occupy, e.g. trapped within the explosive, the system, or vented. The pressure effect on the decomposition rates has been determined for different explosives by using both vented and sealed experiments at low densities. Low-density explosives are usually permeable to decomposition gases and can be used in both vented and sealed configurations to determine pressure-dependent reaction rates. In contrast, explosives that are near the theoretical maximum density (TMD) are not as permeable to decomposition gases, and pressure-dependent kinetics are difficult to determine. Ignition in explosives at high densities can be predicted by using pressure-dependent rates determined from the low-density experiments as long as gas volume changes associated with bulk thermal expansion are also considered. In the current work, cookoff of the plastic-bonded explosives PBX 9501 and PBX 9502 is reviewed and new experimental work on LX-14 is presented. Reactive gases are formed inside these heated explosives causing large internal pressures. The pressure is released differently for each of these explosives. For PBX 9501, permeability is increased and internal pressure is relieved as the nitroplasticizer melts and decomposes. Internal pressure in PBX 9502 is relieved as the material is damaged by cracks and spalling. For LX-14, internal pressure is not relieved until the explosive thermally ignites. The current paper is an extension of work presented at the 26th ICDERS symposium [1].
We have used a modified version of the Sandia Instrumented Thermal Ignition (SITI) experiment to develop a pressure-dependent, five-step ignition model for a plastic bonded explosive (PBX 9501) consisting of 95 wt% octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazoncine (HMX), 2.5 wt% Estane® 5703 (a polyurethane thermoplastic), and 2.5 wt% of a nitroplasticizer (NP): BDNPA/F, a 50/50 wt% eutectic mixture bis(2,2-dinitropropyl)-acetal (BDNPA) and bis(2,2-dinitropropyl)-formal (BDNPF). The five steps include desorption of water, decomposition of the NP to form NO2, reaction of the NO2 with Estane® and HMX, and decomposition of HMX. The model was fit using our experiments and successfully validated with experiments from five other laboratories with scales ranging from about 2 g to more than 2.5 kg of PBX. Our experimental variables included density, confinement, free gas volume, and temperature. We measured internal temperatures, confinement pressure, and ignition time. In some of our experiments, we used a borescope to visually observe the decomposing PBX. Our observations included the endothermic β–δ phase change of the HMX, a small exothermic temperature excursion in low-density unconfined experiments, and runaway ignition. We hypothesize that the temperature excursion in these low density experiments was associated with the NP decomposing exothermically within the PBX sample. This reactant-limited temperature excursion was not observed with our thermocouples in the high-density experiments. For these experiments, we believe the binder diffused to the edges of our high density samples and decomposed next to the highly conductive wall as confirmed by our borescope images.