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.     

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.     

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 Effect of Shear Strain on Texture in Pressed Plastic Bonded Explosives

The insensitive explosive PBX 9502 contains 95 wt‐% of TATB crystals and a plastic bonding agent (Kel‐F). The TATB crystals have plate‐like morphology, similar to that of graphite or boron nitride. We have used X‐ray diffraction to measure the preferred orientation (texture) of the TATB crystals in parts fabricated by pressing PBX 9502 powder. Independently, we have used finite‐element calculations to derive the direction and magnitude of the shear imposed during the consolidation of this composite material. Based on our results, we propose that the texture develops because the applied shear causes the TATB crystals to rotate such that their (002) basal planes are parallel to shear planes. The texture predicted by this model agrees qualitatively with that measured at various locations within the PBX 9502 compact. Further validation of this model is obtained by the measurement of the thermal expansion coefficient of PBX 9502, which is highly anisotropic.     

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.     

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.     

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.     

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.     

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.     

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.     

Tailoring the irreversible thermal expansion of 1,3,5-triamino-2,4,6-trinitrobenzene crystals by bioinspired polydopamine coating

Bioinspired polydopamine (PDA) was selected for the fabrication of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB)-based microcapsules to improve the thermal stability via a facile in situ polymerization of dopamine on the surface of explosive crystals in a weak alkaline aqueous solution. The effects of experimental conditions, including TATB core size, PDA shell content, elevated-temperature hold time, hold temperature, and test stress on the irreversible thermal expansion of TATB crystals, were comprehensively and comparatively studied. After coating, the strain change at each cooling and heating stage in a thermal cycling test from −54 to 74 °C visibly decreased, attributing to the fact that the highly crosslinked and dense PDA shell acted as a rigid pressure vessel to constrain the expansion of energetic crystals. The irreversible expansion strain at room temperature after a 23–113 °C cycle decreased with the increasing of PDA shell thickness. Compared with raw fine grains TATB (FTATB) crystals, FTATB enabled in 1.5 wt % PDA showed a dramatically drop in the irreversible expansion strain at room temperature by 27.7% (from 0.520 to 0.376%). The results demonstrated the excellent ability of PDA to alleviate irreversible thermal expansion of anisotropic energetic crystals. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48695.     

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.     

2,6-二氨基-3,5-二硝基吡啶-1-氧化物基PBX的热安全性研究

为了研究2,6-二氨基-3,5-二硝基吡啶-1-氧化物(ANPyO)基高聚物黏结炸药(PBX)的热安全性,分别以氟橡胶F2311和丁晴橡胶NBR-26为主体设计两种黏结剂体系,采用水悬浮-溶解-蒸馏法制备ANPyO基PBX炸药。利用扫描电子显微镜(SEM)、差示扫描量热法(DSC)和热重法(TG)表征不同黏结剂体系PBX的结构和性能,计算了两种黏结剂体系PBX的热分解动力学参数和热爆炸参数,并获得了被400K气氛环绕的半径为1m的球形、无限圆柱形或无限平板状PBX的热感度概率密度函数S(T)与温度T的关系曲线。结果表明,以丁晴橡胶NBR-26为黏结剂体系主体PBX的活化能E为173.19kJ/mol、指前因子ln(A/s-1)为28.58、自加速分解温度TSADT为550.01K、热点火温度Tbe为565.81K、热爆炸临界温度Tbp为625.06K;以氟橡胶F2311为黏结剂体系主体PBX的活化能E为143.78kJ/mol、指前因子ln(A/s-1)为22.89,自加速分解温度TSADT为539.99K,热点火温度Tbe为560.28K,热爆炸临界温度Tbp为615.55K;球形PBX的热安全性稍高于无限圆柱或平板状PBX,以丁晴橡胶NBR-26为黏结剂体系主体PBX的热安全性高于氟橡胶F2311为黏结剂体系主体PBX。     

Complex Microwave Permittivity of Secondary High Explosives

We aim to understand how microwaves interact with high explosives by studying the complex permittivity from 1–18 GHz of HMX, RDX, TNT, TATB, PETN, Octol, Comp B, 95 % RDX/5 % Viton A (PBX‐RDX), PBX 9404, PBXN‐5, PBXN‐7, PBXW‐14, PBX 9501, and PBX 9502. The combination of a resonant cavity perturbation technique for determining the room‐temperature complex dielectric constant at discrete frequencies and a wide band open circuit method (1–18 GHz) provides an accurate, broadband measurement that describes the dielectric properties in the frequency range of interest. While the values of the real and imaginary permittivity components did not vary significantly as a function of frequency, we found the real part of the permittivity to be highly dependent on relatively small changes in the material density. We used dielectric mixing theory, specifically the linear‐law approximation, to compare the predicted values based on the dielectric properties of individual components with those of the resulting formulation measured experimentally for a select number of samples; the prediction agrees well within the observed variability of the experimentally measured values.     

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.     

Continuous Wave Laser Irradiation of Explosives

Quantitative measurements of the levels of continuous wave (CW) laser light that can be safely applied to bare explosives during contact operations were obtained at 532 nm, 785 nm, and 1550 nm wavelengths. A thermal camera was used to record the temperature of explosive pressed pellets and single crystals while they were irradiated using a measured laser power and laser spot size. A visible light image of the sample surface was obtained before and after the laser irradiation. Laser irradiation thresholds were obtained for the onset of any visible change to the explosive sample and for the onset of any visible chemical reaction. Deflagration to detonation transitions were not observed using any of these CW laser wavelengths on single crystals or pressed pellets in the unconfined geometry tested. Except for the photochemistry of DAAF, TATB and PBX 9502, all reactions appeared to be thermal using a 532 nm wavelength laser. For a 1550 nm wavelength laser, no photochemistry was evident, but the laser power thresholds for thermal damage in some of the materials were significantly lower than for the 532 nm laser wavelength. No reactions were observed in any of the studied explosives using the available 300 mW laser at 785 nm wavelength. Tables of laser irradiance damage and reaction thresholds are presented for pressed pellets of PBX9501, PBX9502, Composition B, HMX, TATB, RDX, DAAF, PETN, and TNT and single crystals of RDX, HMX, and PETN for each of the laser wavelengths.     

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.     

The Effect of Cook‐Off on the Bulk Permeability of a Plastic Bonded Explosive

Plastic bonded explosives when exposed to prolonged heating environments undergo a variety of changes that affect their bulk chemical, thermophysical, and mechanical properties. During slow heating conditions, referred to as cook‐off, the thermal behavior of the polymeric binder plays an important role in the transformations of these composite energetic materials. The recently introduced Darcian flow hypothesis for PBX‐9501 implies that, during preignition, temperature gradients will lead to pressure gradients which in turn will drive convection of decomposition gases throughout the explosive, thus affecting ignition time and location. Here, we focus on the cook‐off behavior of PBX‐9501 and investigate its effects on bulk permeability to gases produced as a result of thermal decomposition. The concept of Darcian convection through porous media is defined and illustrated in detail by the derivation of the governing equations for a permeameter. Based on a systematic analysis involving: 1) our current understanding about binder behavior as a function of temperature, 2) the physics of the gas permeameter apparatus, 3) the concept of liquid drainage by gas, and 4) the experimental record of four permeameter experiments with cooked PBX‐9501, we conclude that samples heated up to 186 °C were not permeable in the Darcy‐flow sense.     

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.     

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.