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.     

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.     

Neutron Diffraction Measurements and Micromechanical Modelling of Temperature‐Dependent Variations in TATB Lattice Parameters

Triaminotrinitrobenzene (TATB) is a highly anisotropic molecular crystal used in several plastic‐bonded explosive (PBX) formulations. TATB‐based explosives exhibit irreversible volume expansion (“ratchet growth”) when thermally cycled. A theoretical understanding of the relationship between anisotropy of the crystal, crystal orientation distribution (texture) of polycrystalline aggregates, and the intergranular interactions leading to this irreversible growth is necessary to accurately develop physics‐based predictive models for TATB‐based PBXs under various thermal environments. In this work, TATB lattice parameters were measured using neutron diffraction during thermal cycling of loose powder and a pressed pellet. The measured lattice parameters help clarify conflicting reports in the literature as these new results are more consistent with one set of previous results than another. The lattice parameters of pressed TATB were also measured as a function of temperature, showing some differences from the powder. This data is used along with anisotropic single‐crystal stiffness moduli reported in the literature to model the nominal stresses associated with intergranular constraints during thermal expansion. The texture of both specimens were characterized and the pressed pellet exhibits preferential orientation of (001) poles along the pressing direction, whereas no preferred orientation was found for the loose powder. Finally, thermal strains for single‐crystal TATB computed from lattice parameter data for the powder is input to a self‐consistent micromechanical model, which predicts the lattice parameters of the constrained TATB crystals within the pellet. The agreement of these model results with the diffraction data obtained from the pellet is discussed along with future directions of research.     

The Effects of TATB Ratchet Growth on PBX 9502

PBX 9502 is a plastic‐bonded explosive that contains 95 wt.‐% TATB, a graphitic‐structured high explosive known to undergo “ratchet growth,” i.e., irreversible volume change that accompanies temperature excursions. Earlier studies have reported changes in TATB‐based composites as a function of thermal cycling and density change, however, a clear distinction between density and ratchet‐growth effects has not been made. In the work reported here, an “as‐pressed density” baseline for the mechanical response of recycled PBX 9502 is established over a density range of interest, then high‐density specimens are thermally cycled between −55 and 80 °C to achieve “ratchet‐grown” parts in the same low‐density region. As‐pressed and ratchet‐grown specimens with identical densities are then analyzed using microX‐ray computed tomography and USANS techniques to obtain information about pore‐size distributions. Data show that after ratchet‐growth, PBX 9502 specimens contain, in general, more numerous and smaller voids than specimens that were pressed with lower compaction pressures to match the same density. The mechanical response of the ratchet‐grown material is consistent with damage, showing lower tensile stress and modulus, lower compressive modulus, and higher tensile and compressive strain, than as‐pressed specimens of the same density.     

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.     

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.     

Fractal Networks of Inter‐Granular Voids in Pressed TATB

Small‐angle neutron scattering techniques were used to study the evolution of void morphology with pressed density of the insensitive high explosive, TATB. Samples were studied as a loose powder and as pressed pellets, ranging in density from approx. 1 to 1.804 g cm⁻³. Inter‐granular voids in the loose powder were randomly arranged (non‐fractal) and had a surface defined mean size of 0.66 μm. Pressing was found to induce a fractal network of voids with fractally rough interfaces. The surface‐defined mean void size of the pressed samples was between 0.21–0.33 μm over the range of densities studied and was found to increase with pressed density up to 1.720 g cm⁻³, decreasing thereafter. The volume fractal dimension, indicative of the void arrangement, mirrored the changes in the mean void size. No systematic change in the surface fractal dimension was found. Surface area analysis allowed the average TATB grain size within the pressed samples to be quantified. An initial decrease of the mean grain size followed by an increase with pressed density suggests that the TATB grains behave in a brittle fashion at low densities and ductile at higher pressed densities.     

Molecular Dynamics Simulations of Polymer‐Bonded Explosives (PBXs): Modeling,Mechanical Properties and their Dependence on Temperatures and Concentrations of Binders

Two models, i.e. “covering” and “cutting” models, for the polymer‐bonded explosives (PBXs) were proposed for different researching aspects. Used for choosing polymeric binders, the “covering” models are mainly applied to find the relations of temperatures and concentrations respectively with elastic properties of the PBXs. The “cutting” model is especially used to describe the highly anisotropic behavior of 1,3,5‐triamino‐2,4,6‐trinitrobenzene crystals (TATB). These models were realized by using molecular dynamics methods. It is found that the ductility of crystalline TATB can be effectively improved by blending fluorine‐containing polymers in small amounts. The moduli for the PBXs decrease with increase in temperature and concentration of binders. Different crystalline surfaces interacting with the same polymer binder have different modulus‐decreasing effects due to the highly anisotropic behavior of TATB. The modulus‐decreasing effect for different crystalline surfaces ranking order is (010)≈(100)>(001).     

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.     

Thermal Expansion of LX‐17, PBX 9502, and Ultrafine TATB

A large quantity of linear strain and LCTE data from −55 °C to 75 °C on LX‐17, PBX 9502 and ultrafine TATB (ufTATB) is presented. Axial and diametral measurements are blended to give final densities, which agree with the liquid immersion values of Baytos et al. The nominal densities at 21, −55 and 75 °C in g ⋅ cm⁻³ are: LX‐17 1.90, 1.920, 1.874; PBX 9502 1.89, 1.907, 1.867; ufTATB 1.80, 1.822, 1.778. Data taken radially show more thermal expansion than that taken transversely in cut‐up parts; both must be combined to get the density. There is no difference between virgin and recycled TATB. Rachet growth data is presented, both at low pressure and at higher pressure, where the swelling is diminished. A Kel‐F strain curve is presented and the theoretical maximum densities are computed.     

Small‐Angle Neutron Scattering and Contrast Variation Measurement of the Interfacial Surface Area in PBX 9501 as a Function of Pressing Intensity

Small‐angle neutron scattering with contrast variation was used to measure the interfacial surface area in a composite high explosive formulated with a deuterated binder. Continuing our work on the effect of varying the pressing intensity on void and binder size distribution, the effect of pressing intensity on the three interfaces (HMX‐binder, HMX‐voids and binder‐voids) of the PBX 9501 microstructure was studied. Formulation of PBX 9501 with a deuterated binder allowed the neutron scattering length density contrast to be varied and thus allowed differentiation of the three interfaces. Porod analysis was used to measure the surface area. The surface area at the interfaces of HMX and binder was found to increase with increasing pressing intensity, while the surface area between HMX and voids may have decreased slightly. No evidence was found for voids within the binder at any pressing intensity.     

Measurement of Porosity in a Composite High Explosive as a Function of Pressing Conditions by Ultra‐Small‐Angle Neutron Scattering with Contrast Variation

We have used ultra‐small‐angle neutron scattering (USANS) with contrast variation to measure the porosity over length scales 0.1–20 μm in a composite high explosive, PBX 9501, formulated with a deuterated binder. Here, we explore the effect of varying the pressing intensity on the PBX 9501 microstructure. Samples of PBX 9501 were die‐pressed with applied pressures ranging between 69 and 200 MPa at 90 °C. Five samples were prepared at each pressure that differed in the fraction of binder that was deuterated, resulting in a change in the neutron scattering length density contrast (Δρ) of the binder relative to that of the high explosive crystallites and voids. By using this approach to discriminate scattering from voids from that due to the binder, we determined microstructure and composition that otherwise would not have been apparent. The sample composition was determined by calculating the Porod Invariant as a function of Δρ and comparing it with compositional estimates obtained from the bulk sample density. Structural modeling of the USANS data, assuming both spherical and cylindrical morphologies, allowed the mean size and size distribution of voids and binder‐filled regions to be determined.     

PBX药柱的不可逆长大对TATB/粘结剂界面粘结性能的影响

研究了热循环对高分子粘结炸药(PBX)药柱的尺寸和力学性能的影响,用扫描电镜观察了断口的形貌.结果表明,PBX药柱在经历反复多次的冷热循环后会出现不可逆的尺寸长大,粘结剂与三氨基三硝基苯(TATB)的界面作用减弱,发生脱粘,材料的抗拉强度也相应下降.     

LX‐17 Corner‐Turning

We have performed a series of highly‐instrumented experiments examining corner‐turning of detonation. A TATB booster is inset 15 mm into LX‐17 (92.5% TATB, 7.5% kel‐F) so that the detonation must turn a right angle around an air well. An optical pin located at the edge of the TATB gives the start time of the corner‐turn. The breakout time on the side and back edges is measured with streak cameras. Three high‐resolution X‐ray images were taken on each experiment to examine the details of the detonation. We have concluded that the detonation cannot turn the corner and subsequently fails, but the shock wave continues to propagate in the unreacted explosive, leaving behind a dead zone. The detonation front farther out from the corner slowly turns and eventually reaches the air well edge 180° from its original direction. The dead zone is stable and persists 7.7 μs after the corner‐turn, although it has drifted into the original air well area. Our regular reactive flow computer models sometimes show temporary failure but they recover quickly and are unable to model the dead zones. We present a failure model that cuts off the reaction rate below certain detonation velocities and reproduces the qualitative features of the corner‐turning failure.     

Microstructural Differences between Virgin and Recycled Lots of PBX 9502

PBX 9502 is an insensitive high explosive formulated comprised of 95 wt% TATB and 5 wt% Kel‐F 800^TM binder. Due to the relatively high cost of manufacturing TATB (triaminotrinitrobenzene), methods for reclaiming TATB from PBX 9502 machine cuttings were previously developed. Reclaimed PBX 9502 was mixed with ~ 50% virgin PBX 9502 to produce “recycled” lots of PBX 9502. Several studies have shown significant differences between the mechanical properties of virgin and recycled lots of PBX 9502, and postulated that the differences were related to various aspects of TATB particle size and distribution. The purpose of this study is to show that these differences in mechanical properties are related to differences in the distribution of TATB within the microstructure of PBX 9502. Ultimately, a better understanding of these properties may lead to selected formulation changes for future rebuilds, Lifetime Extension Programs (LEP) and/or candidate replacements to enhance engineering and physics performance.     

Growth of 1,3,5-Triamino-2,4,6,-Trinitrobenzene (TATB). II. Control of growth by use of high Tg polymeric binders

The remarkable safety characteristics of the high explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) are revolutionizing the design and deployment of nuclear weapons. Kel-F 800 is used as the binder to obtain high-density, mechanically stable billets of TATB that can be machined into desired shapes. However, repeated thermal cycling between − 54 °C and 74 °C of high density, pure, and plastic-bonded TATB billets causes a permanent volume expansion (growth) of about 1.5 vol% to 2.0 vol%. Debonding of the Kel-F 800 binder occurs during growth, causing a reduction in the mechanical properties of the plastic-bonded explosive. The coefficient of thermal expansion (CTE) of these TATB billets between ambient temperature and 74 °C is 67.0 × 10⁻⁶/°C. TATB undergoes a secondary mechanical relaxation just above room temperature, coinciding with the onset of a high CTE, above the glass transition temperature (T_g) of Kel-F 800. Thus, by judicious selection of a high-T_g binder, we have essentially eliminated growth, stopped the degradation of mechanical properties after thermal cycling, suppressed the secondary mechanical relaxation, and lowered the CTE to 50.0 × 10⁻⁶/°C between ambient temperature and 74 °C.     

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].     

Dynamic mechanical signatures of Viton A and plastic bonded explosives based on this polymer

The complex shear moduli of the fluorelastomer Viton A and four plastic bonded explosives LX‐04, LX‐07, LX‐10, and LX‐11, which use this polymer as a binder, have been investigated. LX‐10, LX‐07, LX‐04 and LX‐11 are composites of 94.5, 90, 85 and 80% 1, 3, 5, 7‐tetranitroazacyclooctane (HMX) explosive, respectively, and Viton A. Viton is a random copolymer of 7 vinylidene fluoride and 2 perfluoropropene monomers. In the temperature range from ?150 to 120°C, two relaxations, the β relaxation at ?80°C and the glass transition at ?22°C, were observed as peaks in the loss modulus in Viton A at 0.1 Hz. A third relaxation, T_α, was found above T_g in all four explosive formulations. The plastic bonded explosives (PBX's) showed antiplasticization phenomena. T_g of the explosives increased 2–3°C as the concentration of binder was reduced in 5% steps. Samples from the same original lot of LX‐04 were evaluated after 20–23 years of service. The alpha relaxation occurred at 60°C as a peak in the loss modulus at 1 Hz. Both the beta and alpha relaxations were very broad and an accurate maximum for these relaxations was difficult to determine.     

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.     

A Simple and Rapid Evaluation of Explosive Performance – The Disc Acceleration Experiment

It is crucial in the development of a new explosive to obtain an evaluation of performance early in the process when the availability of material is limited. Evaluation requires dynamic measurements of detonation velocity, pressure, and expansion energy – typically in separate experiments that require large amounts of material, time, and expense. There is also a need for evaluation of the total available thermodynamic energy. The dynamic evaluations, in particular, have been a major hindrance to development of new explosives. The new experimental testing method to be described here requires small charges and obtains accurate measurement of all three of the detonation performance characteristics in a single test. The design, a Disc Acceleration eXperiment (DAX), provides an initial condition of steady detonation and a charge‐geometry amenable to 2D hydrodynamic simulations. The velocity history of a metal disk attached to the end of the explosive charge is measured with Photonic Doppler Velocimetry (PDV). This disc velocity data is analyzed to give both CJ pressure and expansion energy. The detonation velocity is obtained with probes along the charge length. The experiments and subsequent analyses are concentrated on LX‐16, a known PETN based explosive, for the purpose of establishing the accuracy of the method and to provide a standard for comparison with other explosives. We present details of the experimental design and also detonation velocity and PDV results from a number of experiments. The total available internal energy for the explosive was obtained from published detonation calorimetry measurements by Ornellas [1], and from thermodynamic equilibrium calculations. An equation‐of‐state (EOS) for LX‐16 was derived from hydrodynamic simulations of thin plate‐push velocity‐time data. We will show a successful comparison with a previously published Jones‐Wilkins‐Lee (JWL) EOS for PETN by Green and Lee [2–4].