Dead Zones in LX‐17 and PBX 9502

Pin and X‐ray corner turning data have been taken on ambient LX‐17 and PBX 9052, and the results are listed in tables as an aid to future modeling. The results have been modeled at 4 zones/mm with a reactive flow approach that varies the burn rate as a function of pressure. A single rate format is used to simulate failure and detonation in different pressure regimes. A pressure cut‐off must also be reached to initiate the burn. Corner turning and failure are modeled using an intermediate pressure rate region, and detonation occurs at high pressure. The TATB booster is also modeled using reactive flow, and X‐ray tomography is used to partition the ram‐pressed hemisphere into five different density regions. The model reasonably fits the bare corner turning experiment but predicts a smaller dead zone with steel confinement, in contradiction with experiment. The same model also calculates the confined and unconfined cylinder detonation velocities and predicts the failure of the unconfined cylinder at 3.75 mm radius. The PBX 9502 shows a smaller dead zone than LX‐17. An old experiment that showed a large apparent dead zone in Composition B was repeated with X‐ray transmission and no dead zone was seen. This confirms the idea that a variable burn rate is the key to modeling. The model also produces initiation delays, which are shorter than those found in time‐to‐detonation.     

Air Gaps,Size Effect,and Corner‐Turning in Ambient LX‐17

Various measurements under ambient conditions are presented for LX‐17. The size (diameter) effect has been measured with copper and Lucite confinement, where the failure radii are 4.0 and 6.5 mm, respectively. The air well corner‐turning has been measured with an LX‐07 booster, and the dead‐zone results are comparable to the previous TATB‐boosted work. Four double cylinders have been fired, and dead zones appear in all cases. The steel‐backed samples are faster than the Lucite‐backed samples by 0.6 μs. Bare LX‐07 and LX‐17 charges of 12.7 mm radius were fired with air gaps. Long acceptor regions were used to truly determine if detonation occurred or not. The LX‐07 booster crossed a 10 mm gap with a slight time delay. Steady‐state LX‐17 crossed a 3.5 mm gap but failed to cross a 4.0 mm gap. LX‐17 charge with a 12.7 mm radius run after the booster crossed a 1.5 mm gap but failed to cross a 2.5 mm gap. Timing delays were measured where the detonation crossed the gaps. The Tarantula model is introduced as embedded in reactive flow JWL++and Linked Cheetah V4, mostly at 4 zones mm⁻¹. Tarantula has four pressure regions: off, initiation, failure, and detonation. The physical basis of the input parameters is considered.     

Ignition and Growth Modeling of LX‐17 Hockey Puck Experiments

Detonating solid plastic bonded explosives (PBX) formulated with the insensitive molecule triaminotrinitrobenzene (TATB) exhibit measurable reaction zone lengths, curved shock fronts, and regions of failing chemical reaction at abrupt changes in the charge geometry. A recent set of “hockey puck” experiments measured the breakout times of diverging detonation waves at ambient temperature LX‐17 (92.5% TATB plus 7.5% Kel‐F binder) and the breakout times at the lower surfaces of 15 mm thick LX‐17 discs placed below the detonator‐booster plane. The LX‐17 detonation waves in these discs grow outward from the initial wave leaving regions of unreacted or partially reacted TATB in the corners of these charges. This new experimental data is accurately simulated for the first time using the Ignition and Growth reactive flow model for LX‐17, which is normalized to detonation reaction zone, failure diameter and diverging detonation data. A pressure‐cubed dependence for the main growth of reaction rate yields excellent agreement with experiment, while a pressure‐squared rate diverges too quickly and a pressure‐quadrupled rate diverges too slowly into the LX‐17 below the booster equatorial plane.     

Corner Turning of Detonation Waves in an HMX‐based Paste Explosive

Detonation wave profiles have been determined for RX‐08‐HD (74% HMX paste) loaded in 3 mm square troughs after turning both acute 90° bends and bends with a 1.5 mm inner radius turn and a 4.5 mm outer radius. The explosive troughs were confined with either lucite or copper. We show that the shape of the detonation wavefront can be explained in terms of a Huygens' construction from the leading point to the outer radius. Turbulent behavior occurs between the leading point and the inner edge. The turbulence appears enhanced for the curved samples with copper confinement. The distance the detonation wave has to travel past the turn in order to regain its original symmetry was found to be governed by an exponential time constant of 0.6 µs. Analysis suggests that the leading point alone stays at the straight‐ahead detonation velocity throughout the turn.     

Changes in Pore Size Distribution upon Thermal Cycling of TATB‐based Explosives Measured by Ultra‐Small Angle X‐Ray Scattering

Hot‐spot models of initiation and detonation show that voids or porosity ranging from nanometer to micrometer in size within highly insensitive energetic materials affect initiability and detonation properties. Thus, the knowledge of the void size distribution, and how it changes with the volume expansion seen with temperature cycling, are important to understanding the properties of the insensitive explosive 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB). In this paper, void size distributions in the 2 nm to 2 μm regime, obtained from small‐angle X‐ray scattering measurements, are presented for LX‐17‐1, PBX‐9502, and ultra‐fine TATB formulations, both as processed and after thermal cycling. Two peaks were observed in the void size distribution: a narrow peak between 7–10 nm and a broad peak between 20 nm and about 1 mm. The first peak was attributed to porosity intrinsic to the TATB crystallites. The larger pores were believed to be intercrystalline, a result of incomplete consolidation during processing and pressing. After thermal cycling, these specimens showed an increase in both the number and size of these larger pores. These results illuminate the nature of the void distributions in these TATB‐based explosives from 2 nm to 2 μm and provide empirical experimental input for computational models of initiation and detonation.     

Highly Thermal Stable TATB‐based Aluminized Explosives Realizing Optimized Balance between Thermal Stability and Detonation Performance

In this work, a series of TATB‐based aluminized explosives were formulated from 1, 3, 5‐triamino‐2, 4, 6‐trinitrobenzene (TATB), aluminum powders and polymeric binders. The thermal stability, heat of detonation, detonation velocity and pressure of the TATB based aluminized (TATB/Al) explosives were systematically investigated by cook‐off, constant temperature calorimeter, electrometric method and manganin piezo resistance gauge, respectively. The selected PBX‐3 (70 wt% TATB/25 wt% Al/5 wt% fluorine resin) achieved optimized balance between thermal stability and detonation performance, with the thermal runaway temperature around 583 K. The thermal ignition of TATB‐based aluminized explosive occurred at the edge of the cylinder according to the experimental and numerical simulations. Moreover, the critical thermal runaway temperature for PBX‐3 was calculated based on the Semenov's thermal explosion theory and the thermal decomposition kinetic parameters of the explosive, which was consistent with the experimental value.     

The Microstructure of TATB‐Based Explosive Formulations During Temperature Cycling Using Ultra‐Small‐Angle X‐Ray Scattering

TATB (1,3,5 triamino‐2,4,6‐trinitrobenzene), an extremely insensitive explosive, is used both in polymer‐bound explosives (PBXs) and as an ultra‐fine pressed powder (UFTATB). Many TATB‐based explosives, including LX‐17, a mixture of TATB and Kel‐F 800 binder, experience an irreversible expansion with temperature cycling known as ratchet growth. Additional voids, with sizes hundreds of nanometers to a few micrometers, account for much of the volume expansion. Measuring these voids is important feedback for hot‐spot theory and for determining the relationship between void size distributions and detonation properties. Also, understanding mechanisms for ratchet growth allows future choice of explosive/binder mixtures to minimize these types of changes, further extending PBX shelf life. This paper presents the void size distributions of LX‐17, UFTATB, and PBXs using commercially available Cytop M, Cytop A, and Hyflon AD60 binders during temperature cycling between −55 and 70 °C. These void size distributions are derived from ultra‐small‐angle X‐ray scattering (USAXS), a technique sensitive to structures from about 2 nm to about 2 μm. Structures with these sizes do not appreciably change in UFTATB. Compared to TATB/Kel‐F 800, Cytop M and Cytop A show relatively small increases in void volume from 0.9 to 1.3% and 0.6 to 1.1%, respectively, while Hyflon fails to prevent irreversible volume expansion (1.2–4.6%). Computational mesoscale models combined with experimental results indicate both high glass transition temperature as well as TATB binder adhesion and wetting are important to minimize ratchet growth.     

Experimental study and numerical simulation of the corner turning of TATB based and CL-20 based polymer bonded explosives

In order to study the corner turning performance of detonation waves for TATB (1,3,5-triamino-2,4,6-trinitrobenzene) based and CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12- hexaazaisowurtzitane) based polymer bonded explosives (PBXs with PBX-I, PBX-II, and PBX-III modifications), mushroom tests are used to obtain the first breakout angles, failure angles, and delay times with initiating diameters of 10 and 15 mm. The results show that these parameters of PBX-I increase with an increase in the initiating diameter. The first breakout angles and failure angles of PBX-II and PBX-III are 90? for the initiating diameter of 10 mm, while these angles for PBX-I are 22.7 and 31.9? for the same initiating diameter, which implies that CL-20 based explosives have excellent corner turning performance, even with 13.5 wt.% aluminum powders added to PBX-III. Then, two-dimensional numerical simulations of PBX-I are performed by using the Lee–Tarver ignition and growth model. The computed results agree well with the measured results for all cases studied.     

Crystal Morphology Controlling of TATB by High Temperature Anti‐Solvent Recrystallization

The spheroidizing of TATB (1,3,5‐triamino‐2,4,6‐trinitrobenzene) can help to control preferred orientation and anisotropic expansion of TATB based PBXs, as well as to improve crystal quality, desensitizing efficiency, packing density, and even explosive energy. In this paper, TATB crystals with different morphology were obtained by high temperature recrystallization from anti‐solvents. TATB was dispersed into DMSO and heated to dissolve. Water as an anti‐solvent was added to the solution with different conrol parameters. We designed additional experiments to study the particular influence of these parameters. It was shown that the crystal morphology is strongly affected by the stirring rate and the amount of water added. The recrystallized TATB samples have similar thermal stability as starting TATB, but higher densities and purities, which indicates that the quality of TATB crystals was improved. By slowly adding an appropriate amount of water and cooling, regular crystals of TATB were obtained, which proves that water is a good morphology modifier for TATB.     

Structural Defect Evolution of TATB‐Based Compounds Induced by Processing Operations and Thermal Treatments

2,4,6‐Triamino‐1,3,5‐trinitrobenzene (TATB) compounds are commonly used in high performance explosives because of their thermal stability and high detonation velocities compared to other materials. The insensitivity and mechanical properties are related to the stability of their crystalline structure. Crystallographic structure and structural defects evolution of TATB and TATB‐based compounds were studied by X‐ray diffraction for powders, molding powders, and pressed compounds, using Rietveld refinement. The effects of synthesis conditions, thermal treatments, coating and pressing operations on the structure of TATB compounds were evaluated. The results show that the pressing operation results in anisotropic crystallite size, leading to an increase of the structural defects density. It could be due to the anisotropic mechanical response of the TATB crystal under pressure, possibly plasticity. Finally, it is shown that increasing thermal treatment temperature on TATB powders decreases the structural defects density.     

Laboratory‐Scale Method for Estimating Explosive Performance from Laser‐Induced Shock Waves

A new laboratory‐scale method for predicting explosive performance (e.g., detonation velocity and pressure) based on milligram quantities of material is demonstrated. This technique is based on schlieren imaging of the shock wave generated in air by the formation of a laser‐induced plasma on the surface of an energetic material residue. The shock wave from each laser ablation event is tracked for more than 100 μs using a high‐speed camera. A suite of conventional energetic materials including DNAN, TNT, HNS, TATB, NTO, PETN, RDX, HMX, and CL‐20 was used to develop calibration curves relating the characteristic shock velocity for each energetic material to several detonation parameters. A strong linear correlation between the laser‐induced shock velocity and the measured performance from full‐scale detonation testing has been observed. The Laser‐induced Air Shock from Energetic Materials (LASEM) method was validated using nitrocellulose, FOX‐7, nano‐RDX, three military formulations, and three novel high‐nitrogen explosives currently under development. This method is a potential screening tool for the development of new energetic materials and formulations prior to larger‐scale detonative testing. The main advantages are the small quantity of material required (a few milligrams or less per laser shot), the ease with which hundreds of measurements per day can be obtained, and the ability to estimate explosive performance without detonating the material (reducing cost and safety requirements).     

Reaction Zones in Ultrafine TATB

We have measured the particle velocity of aluminum foils placed between ultrafine TATB and lithium fluoride, where the TATB thicknesses are varied between 0 and 8 mm. Resolution is about ±2 ns. The reaction zones are determined from the data, with 0.3 mm being the average. We suggest a 1‐D analytical approach based on the idea that the initiating flyer must put in some minimum amount of energy over one reaction zone length. The energy is calculated three ways: flyer input, reaction zone to be filled and the P²τ initiation energy. Code calculations show the reaction zones rapidly growing in the region dominated by the flyer followed by a slow increase as the detonation takes hold.     

Enhancement of Creep Properties of TATB‐Based Polymer‐Bonded Explosive Using Styrene Copolymer

In order to investigate the effects of binder component on the creep properties of polymer‐bonded explosive (PBX), three‐point bending creep behaviors of 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB)‐based PBX and its styrene copolymer modified formulation were studied by dynamic mechanical analyzer. The experimental results showed that owing to the addition of reinforcing agent (styrene copolymer) with high glass transition temperature and high mechanical strength, the creep resistance performance of the modified formulation was improved with reduced creep strain and constant creep rate and prolonged creep failure time. A six‐element mechanical model was applied to simulate the creep behaviors of TATB‐based PBX and its modified formulation. The constitutive equation of creep curves under different conditions were obtained by nonlinear fit. The predicted theoretical results coincided quite well with the experimental data.     

PBX-9404和PBX-9502炸药拐角性能的数值模拟

借助于有限元动力学软件LS-DYNA,通过Mushroom试验模拟,研究了PBX-9404和PBX-9502的拐角性能.结果显示,在相同试验条件下,PBX-9502的出射角小于PBX-9404,PBx-9502具有明显的死区,表明PBx-9404的拐角性能优于PBx-9502.传爆药直径和炸药半球直径变化对表征炸药拐角...     

Initiation Pressure Thresholds from Three Sources

Pressure thresholds are minimum pressures needed to start explosive initiation that ends in detonation. We obtain pressure thresholds from three sources. Run‐to‐detonation times are the poorest source but the fitting of a function gives rough results. Flyer‐induced initiation gives the best results because the initial conditions are the best known. However, very thick flyers are needed to give the lowest, asymptotic pressure thresholds used in modern models and this kind of data is rarely available. Gap test data are in much larger supply but the various test sizes and materials are confusing. We find that explosive pressures are almost the same if the distance in the gap test spacers are in units of donor explosive radius. Calculated half‐width time pulses in the spacers may be used to create a pressure‐time curve similar to that of the flyers. The very‐large Eglin gap tests give asymptotic thresholds comparable to extrapolated flyer results. The three sources are assembled into a much‐expanded set of near‐asymptotic pressure thresholds. These thresholds vary greatly with density: for TATB/LX‐17/PBX 9502, we find values of 4.9 and 8.7 GPa at 1.80 and 1.90 g/cm³, respectively.     

Time‐Evolution of TATB‐Based Irreversible Thermal Expansion (Ratchet Growth)

TATB is an insensitive high explosive, attractive for use because of its safety aspects. TATB compactions, with or without binder, undergo irreversible volume expansion (or ratchet growth) upon thermal cycling. In the past, experimental elucidation of this phenomenon has focused on irreversible expansion as a function of the number of thermal excursions over a given temperature range, where growth is asymptotic with increasing cycle number. In this paper, we demonstrate that ratchet growth also occurs as a function of time at constant temperature, and that growth is substantial at elevated temperatures. We have measured strain response in PBX 9502, a TATB‐based composite, by performing thermal‐cycling tests with different durations at high temperature. Irreversible growth arises from the thermal ramps themselves (increasing and decreasing), as well as from the subsequent isotherms. PBX 9502 specimens with previously‐identified TATB texture/orientation were used in order to eliminate and/or evaluate texture as a variable. Measurements were also performed on dry‐pressed TATB (no binder) to confirm that expansion as a function of time (constant temperature) is not caused by the binder. A simple analysis of the time‐response data demonstrates consistency in the results. We propose that the primary driving force for irreversible expansion is the proximity of the current strain value (due to thermal history) to the strain saturation point of the current cycle (i.e. strain at infinite high‐temperature hold times or an infinite number of cycles). Such tests should aid in the understanding and modeling of ratchet growth response in these materials.     

Insensitive High Explosives II: 3,3′‐Diamino‐4,4′‐azoxyfurazan (DAAF)

This paper reviews the synthesis, properties, performance, and safety of the insensitive explosive 3,3′‐diamino‐4,4′‐azoxyfurazan (DAAF, C₄H₄N₈O₃), CAS‐No. [78644‐89‐0], and 18 formulations based on it. Though having a moderate crystal density only, DAAF offers high positive heat of formation and hence superior performance when compared with TATB. It is friction and impact insensitive but is more sensitive to shock than TATB and has an exceptionally small critical diameter and performs very well at low temperatures unlike other insensitive explosives. 39 references to the public domain are given. For Part I see Ref. [1].     

Preparation and Properties Study of Core‐Shell CL‐20/TATB Composites

The insensitive high explosive 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB) was selected for coating and desensitization of hexanitrohexaazaisowurtzitane (CL‐20), another high explosive, after surface modification. About 2 wt‐% polymer binder was adopted in the preparation process to further maintain the coating strength and fill the voids among energetic particles. The structure, sensitivity, polymorph properties, and thermal behavior of CL‐20/TATB by coating and physical mixing were studied. Scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS) results indicate that submicrometer‐sized TATB was compactly coated onto the CL‐20 surface with coverage close to 100 %. The core‐shell structure of CL‐20/TATB was confirmed by observation of hollow TATB shell from the CL‐20 core dissolved sample. X‐ray diffraction (XRD) analysis revealed that the polymorph of CL‐20 maintained ε form during the whole preparing process. Thermal properties were studied by thermogravimetry (TG) and differential scanning calorimeter (DSC), showing effects of TATB coating on the polymorph thermal stability and exothermic decomposition of CL‐20. Both the impact and friction sensitivities were markedly reduced due to the cushioning and lubricating effects of TATB shell. The preparation of explosive composites with core‐shell structure provides an efficient route for the desensitization of high explosives, such as CL‐20 in this study.     

Damage of a High‐Energy Solid Propellant and Its Deflagration‐to‐Detonation Transition

In order to assess the safety of high‐energy solid propellants, the effects of damage on deflagration‐to‐detonation transition (DDT) in a nitrate ester plasticized polyether (NEPE) propellant, is investigated. A comparison of DDT in the original and impacted propellants was studied in steel tubes with synchronous optoelectronic triodes and strain gauges. The experimental results indicate that the microstructural damage in the propellant enhances its transition rate from deflagration to detonation and causes its increased sensitivity. It is suggested that the mechanical properties of the propellant should be improved to reduce its damage so that the probability of DDT might be reduced.     

Preparation and Characterization of Nano‐TATB Explosive

Nano‐TATB was prepared by solvent/nonsolvent recrystallization with concentrated sulfuric acid as solvent and water as nonsolvent. Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM) were used to characterize the appearance and the size of the particles. The results revealed that nano‐TATB particles have the shape of spheres or ellipsoids with a size of about 60 nm. Due to their small diameter and high surface energy, the particles tended to agglomerate. By using X‐ray powder diffraction (XRD), broadening of diffraction peaks and decreasing intensity were observed, when the particle sizes decreases to the nanometer size range. The corrected average particle size of nano‐TATB was estimated using the Scherrer equation and the size ranged from 27 nm to 41 nm. Furthermore, the specific surface area and pore diameter of nano‐TATB were determined by BET method. The values were 22 m²/g and 1.7 nm respectively. Thermogravimetric (TG) and Differential Scanning Calorimetric (DSC) curves revealed that thermal decomposition of nano‐TATB occurs in the range of 356.5 °C–376.5 °C and its weight loss takes place at about 230 °C. Furthermore, a slight increase in the weight loss was observed for nano‐TATB in comparison with micro‐TATB.