Preparation and Properties of HMX Coated with a Composite of TNT/Energetic Material

To improve the safety of HMX without sacrificing energy properties, the composites of TNT and an energetic material (HP‐1) were used to coat HMX particles by a method of integrating solvent–nonsolvent with aqueous suspension‐melting. SEM (scanning electron microscopy) and XPS (X‐ray photoelectron spectrometry) were employed to characterize the samples. The effect of the processing parameters, such as mass ratio of HP‐1 to TNT (MRHT), stirring speed, and cooling rate, on the quality of coated samples were investigated and discussed. The mechanical sensitivity, thermal sensitivity, thermal decomposition characteristic, and heat of detonation of raw and coated HMX samples were also measured and contrasted. Results show that when MRHT, stirring speed in the second stage and cooling rate are 1 : 5, 1000 r⋅min⁻¹ and 5 °C⋅min⁻¹ respectively, the optimal coating effect is achieved. Compared with that of raw HMX, both impact and friction sensitivity of HMX coated with 2.5 wt.‐% TNT and 0.5 wt.‐% HP‐1 decrease obviously, whereas there is a slight change in their thermal sensitivity and thermal decomposition characteristics. Meanwhile, such surface coating does not result in the decrease of its energy properties.     

The Synthesis and Energetic Properties of 5,7‐Dinitrobenzo‐1,2,3,4‐tetrazine‐1,3‐dioxide (DNBTDO)

Energetic tetrazine‐1,3‐dioxide, 5,7‐dinitrobenzo‐1,2,3,4‐tetrazine‐1,3‐dioxide ( DNBTDO ), was synthesized in 45 % yield. DNBTDO was characterized as an energetic material in terms of performance (V_det 8411 m s⁻¹; p_{C J} 3.3×10¹⁰ Pa at a density of 1.868 g cm⁻³), mechanical sensitivity (impact and friction as a function of grain size), and thermal stability (T_dec 204 °C). DNBTDO exhibits a sensitivity slightly higher than that of RDX , and a performance slightly lower (96 % of RDX ).     

The Facile Synthesis and Energetic Properties of an Energetic Furoxan Lacking Traditional “Explosophore” Moieties: (E,E)‐3,4‐bis(oximomethyl)furoxan (DPX1)

Energetic furoxan (E,E)‐3,4‐bis(oximomethyl)furoxan (DPX1) was synthesized in 75 % yield, using a literature procedure, from a precursor readily available in one step from nitromethane. DPX1 was characterized for the first time as an energetic material in terms of calculated performance (V_det = 8245 m s⁻¹; p_C‐J = 29.0 GPa) and measured sensitivity (impact: 10 J; friction: 192 N; T_dec: 168 °C). DPX1 exhibits a sensitivity less than that of RDX, and a performance significantly higher than 2,4,6‐trinitrotoluene (TNT).     

Preparation of Nano‐Structured RDX in a Silica Xerogel Matrix

RDX is preferred as explosive in munitions due to its balance of power and sensitivity that is known to be dependent on its particle size and size distribution. In this study, we prepared nano‐sized RDX in a silica xerogel matrix using a sol‐gel method and investigated its sensitivity for explosive properties. The presence of RDX in composite xerogel was confirmed by TG‐DSC and FTIR techniques. Microstructure and porosity were characterized by transmission electron microscopy (TEM), small angle X‐ray scattering, and N₂‐physisorption techniques. TEM results showed that the size of RDX particles in the RDX‐silica composites is in the range of 10–30 nm. The sensitivity to impact and friction was found to be higher for the composites compared to raw RDX. It was also found to be significantly dependent on the acetone/TMOS ratio used in the preparation.     

Characterization of 4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine

4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine (DANT) was prepared with a 35 % yield from cyanuric chloride in a three step process. DANT was characterized by IR and NMR spectroscopy (¹H, ¹³C, ¹⁵N), single‐crystal X‐ray diffraction, and DTA. The crystal density of DANT is 1.849 g cm⁻³. The cyclization of one azido group and one nitrogen atom of the triazine group giving tetrazole was observed for DANT in a dimethyl sulfoxide solution using NMR spectroscopy. An equilibrium exists between the original DANT molecule and its cyclic form at a ratio of 7 : 3. The sensitivity of DANT to impact is between that for PETN and RDX, sensitivity to friction is between that for lead azide and PETN, and sensitivity to electric discharge is about the same as for PETN. DANT′s heat of combustion is 2060 kJ mol⁻¹.     

氧化石墨烯对RDX/PMMA安全性能及力学性能影响

为改善RDX的安全性能和力学性能,采用乳液聚合法制备RDX/聚甲基丙烯酸甲酯/氧化石墨烯(RDX/PMMA/GO)微球,并用相同方法制备了RDX/PMMA复合粒子进行对比;通过扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FT-IR)和差示扫描热量仪(DSC)对样品进行表征,并测试其撞击感度和药柱的静态力学性能。结果表明,包覆后RDX/PMMA微球形貌趋于球形,RDX/PMMA/GO粒子存在明显的层状皱褶;RDX晶型均未发生改变;与原料RDX和RDX/PMMA相比,RDX/PMMA/GO微球的表观活化能分别提高22.16kJ/mol和15.17kJ/mol,升温速率趋近于0时的峰温和热爆炸临界温度与原料RDX相比分别提升6.45℃和6.23℃;特性落高由包覆前的26.74cm分别提至62.95cm和78.52cm,撞击感度明显降低。RDX/PMMA/GO抗压强度比RDX/PMMA增加了7.5MPa,表明GO的加入对复合材料的力学性能提升明显。     

The Effect of RDX Crystal Defect Structure on Mechanical Response of a Polymer‐Bonded Explosive

An explosive composition, derived from AFX‐757, was systematically varied by using three different qualities of Class I RDX. The effect of internal defect structure of the RDX crystal on the shock sensitivity of a polymer bonded explosive is generally accepted (Doherty and Watt, 2008). Here the response to a mechanical non‐shock stimulus is studied using an explosion‐driven deformation test as well as the ballistic impact chamber. No correlation between RDX crystal quality and deformation sensitivity is observed. The DDT behavior (Deflagration to Detonation Transition) of the three plastic bonded explosives, although similar in composition, is distinct regarding the rate of diameter increase in the explosion‐driven deformation test. Recovered polymer bonded explosive from the explosion‐driven deformation test responds equally fast or slower in the ballistic impact chamber. Based on our experimental results the shear rate threshold as a single parameter describing mechanical sensitivity is challenged, and preference is given to the development of an ignition criterion based on inter‐granular sliding friction under the action of a normal pressure.     

Formation and Characterization of Nano‐sized RDX Particles Produced Using the RESS‐AS Process

It has been shown that nano‐sized particles of secondary explosives are less sensitive to impact and can alter the energetic performance of a propellant or explosive. In this work the Rapid Expansion of a Supercritical Solution into an Aqueous Solution (RESS‐AS) process was used to produce nano‐sized RDX (cyclo‐1,3,5‐trimethylene‐2,4,6‐trinitramine) particles. When a saturated supercritical carbon dioxide/RDX solution was expanded into neat water, RDX particles produced from the RESS‐AS process agglomerated quickly and coarsened through Ostwald ripening. However, if the pH level of the suspension was changed to 7, particles were metastably dispersed with a diameter of 30 nm. When the supercritical solution was expanded into air under the same pre‐expansion conditions using the similar RESS process, RDX particles were agglomerated and had an average size of approximately 100 nm. Another advantage of using a liquid receiving solution is the possibility for coating energetic particles with a thin layer of polymer. Dispersed particles were formed by coating the RDX particles with the water soluble polymers polyvinylpyrrolidone (PVP) or polyethylenimine (PEI) in the RESS‐AS process. Both PVP and PEI were used because they have an affinity to the RDX surface. Small and well‐dispersed particles were created for both cases with both PVP and PEI‐coated RDX particles shown to be stable for a year afterward. Several benefits are expected from these small polymer coated RDX particles such as decreased sensitivity, controlled reactivity, and enhanced compatibility with other binders for fabrication of bulk‐sized propellants and/or explosives.     

Preparation and Properties of an AP/RDX/SiO2 Nanocomposite Energetic Material by the Sol‐Gel Method

A nanocomposite energetic material was prepared using sol‐gel processing. It was incorporated into the nano or submicrometer‐sized pores of the gel skeleton with a content up to 95 %. AP, RDX, and silica were chosen as the energetic crystal and gel skeleton, respectively. The structure and its properties were characterized by SEM, BET methods, XRD, TG/DSC, and impact sensitivity measurements. The structure of the AP/RDX/SiO₂ cryogel is of micrometer scale powder with numerous pores of nanometer scale and the mean crystal size of AP and RDX is approx. 200 nm. The specific surface area of the AP/RDX/SiO₂ cryogel is 36.6 m² g⁻¹. TG/DSC analyses indicate that SiO₂ cryogel can boost the decomposition of AP and enhance the interaction between AP and RDX. By comparison of the decomposition heats of AP/RDX/SiO₂ at different mass ratios, the optimal mass ratio was estimated to be 6.5/10/1 with a maximum decomposition heat of 2160.8 J g⁻¹. According to impact sensitivity tests, the sensitivity of the AP/RDX/SiO₂ cryogel is lower than that of the pure energetic ingredients and their mixture.     

Efficient Sensitivity Reducing and Hygroscopicity Preventing of Ultra‐Fine Ammonium Perchlorate for High Burning‐Rate Propellants

In this research, several inert materials, including some functional carbon materials, paraffin wax and the well‐known insensitive energetic material 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB) were selected to reduce the undesirable high sensitivity and hygroscopicity of ultra‐fine ammonium perchlorate (UF‐AP) via polymer modified coating. Structure, sensitivity, thermal and hygroscopicity performances of the UF‐AP based composites were systematically studied by scanning electron microscopy, sensitivity tests, thermal experiments, contact angle, and hygroscopicity analysis. The results showed that both the impact and friction sensitivity of UF‐AP can be remarkably reduced, respectively, with only a small amount of 2 % (in mass) desensitization agents. Meanwhile, improved thermal decomposition was gained, and the hygroscopicity can also be reduced to a large extent. Propellants containing 10 % coated UF‐AP in mass were processed and tested, the burning rate reached 45.7 mm s⁻¹, 50 % higher compared with that of normal AP, with remarkably reduced impact sensitivity from 11.5 J to 29.6 J and friction sensitivity from 76 % to 28 %.     

Effect of Different Polymeric Matrices on Some Properties of Plastic Bonded Explosives

Matrices based on polyisobutylene (PIB), polymethyl‐methacrylate (PA), Viton A 200, Dyneon FT 2481 (Fluorel), and polydimethyl‐siloxane binders were studied as desensitizers. A series of plastic explosives (PBXs) were prepared, based on four different nitramines, namely RDX (1,3,5‐trinitro‐1,3,5‐triazinane), β‐HMX (β‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane), BCHMX (cis‐1,3,4,6‐tetranitro‐octahydroimidazo‐[4,5‐d]imidazole) and ε‐HNIW (ε‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane, ε‐CL‐20), bonded by the matrices mentioned. For comparison, pentaerythritol tetranitrate and certain commercial explosives based on it, Semtex 1A, Semtex 10 and Sprängdeg m/46, were used. Detonation velocities, sensitivities to impact and friction, and peak temperatures of thermal decomposition by differential thermal analysis technique (DTA) for all the explosives studied were determined. Heat of detonation was calculated by means of a thermodynamic calculation program (EXPLO 5 code). Fluoroelastomers have a neutral to positive effect on the thermal stability of nitramines and they have a significant effect on decreasing the friction sensitivity. However, their anti‐impact efficiency is the lowest in this study although they have a positive effect on performance of the corresponding PBXs. PA and PIB matrices markedly decrease thermal stability of nitramines, the anti‐impact influences of PIB‐binders are better than those of PA‐binders, while PA‐binders have a higher anti‐friction effect and slightly less negative influence on the performance of the PBXs in comparison with PIB mixtures. The polydimethyl‐siloxane matrix has a neutral effect on thermal stability of the nitramines studied, it has an influence on the volume thermochemistry of detonation comparable with that of fluoroelastomers although it does not provide comparable performance, and its corresponding PBXs have optimum sensitivity parameters.     

Dependence of the Mechanical Sensitivity on the Fractal Characteristics of Octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine Particles

Three fabrication methods were used to synthesize HMX powders with different particle sizes and microscopic morphologies. All as‐prepared samples were characterized by laser granularity measurements and scanning electron microscopy (SEM). The mechanical sensitivity and thermal stability of the different HMX powders were characterized using mechanical sensitivity tests and differential scanning calorimetry (DSC). Size distribution data and SEM images were used to find the size fractal dimension (D) and surface fractal dimension (D_s) of HMX samples, which were calculated by the least‐squares method and fractal image processing software (FIPS), respectively. The parameters D and D_s quantize two important properties of HMX particles, namely the complexity of the particle size distribution and the irregularity of the particle surface, which affect the thermal conductivity of the particle group if it is exposed to stimuli such as impact, friction or heating. The fractal dimensions reveal the dependence of the mechanical sensitivity of HMX on the powder size, size distribution and microscopic morphology. The results indicate that the proportion of fine particles in HMX powder increases as the D value increases, which causes decreased impact sensitivity. This occurs because hot spot formation leading to an explosion is more difficult because of the improved thermal conductivity of the particle group. Similarly, the surface roughness of HMX particles increases with an increase in D_s, causing an increase in friction sensitivity because of the excessive accumulation of frictional heat. In addition, thermal analysis results indicate that the maximum thermal decomposition rate of HMX decreases with increasing D and D_s.     

CL-20/TATB混合物的制备及性能表征

为了提高六硝基六氮杂异伍兹烷(CL-20)的安全性,采用机械混合法和重结晶法分别制备了CL-20/TATB混合物;通过光学显微镜、扫描电子显微镜(SEM)、X-射线衍射(XRD)、差示扫描量热仪(DSC)、感度测试仪对其形貌、晶型、热稳定性、机械感度进行测试分析。结果表明,机械混合后CL-20表面无明显包覆物,而重结晶混合粒子表面有一层致密的黄色薄膜,同时两种混合物中CL-20的晶型仍为ε型,未发生晶型转变;两种混合物的热分解表观活化能较原料CL-20分别提高了17.3、117.36kJ/mol,热爆炸临界温度分别提高了0.12、3.8℃,重结晶混合粒子的热稳定性明显提高;两种混合物的撞击感度(H50)较原料CL-20分别提高了10.4、54.5cm,摩擦感度的临界载荷分别提高了80、60N,表明重结晶混合粒子的机械感度显著降低。     

Preparation and Properties of a nRDX‐based Propellant

The incorporation of nano‐scaled cyclotrimethylene trinitramine (nRDX) in nitrocellulose (NC)‐based propellants poses processing problems when following conventional methods. Hence, a new preparation method containing a pre‐dispersion process was developed, by which 30 mass % RDX (290 nm) was incorporated in the propellant. Meanwhile, the corresponding 290 nm, 12.85 μm and 97.76 μm RDX‐based propellants were prepared for comparison using a conventional method. The morphology, structure, ballistic and mechanical properties of the prepared propellants were characterized by scanning electron microscopy (SEM), density analyzer, closed vessel (CV), uniaxial tensile tester and impact tester. The results indicate that the nRDX particles were uniformly dispersed in the NC/NG/TEGDN matrix using the novel method, while agglomerated and recrystallized into large particles with the conventional method. The propellant density increased with decreasing RDX particle size. In particular, the 290 nm RDX‐based propellant exhibited a higher burning rate and lower average pressure exponent (α =0.958) compared to the 12.85 μm RDX‐based propellant (α =1.043). The tensile strength, elongation at break and impact strength of the RDX‐based propellant at −40 °C, 20 °C and 50 °C were dramatically improved by using 290 nm RDX with the novel method.     

Preparation,Characterisation and Performance of Microencapsulated Red Phosphorus

Microencapsuled red phosphorus (MRP), with a phenolic resin coating layer, was successfully prepared. It was characterized by Fourier‐transform infrared spectroscopy (FTIR) and Scanning electron microscope (SEM). Meanwhile its water absorption, thermostability, thermodynamic properties and critical ignition temperature (T _b) have been studied. The results show that the MRP which is coated with phenolic resin can decrease the water absorption, increase thermostability and critical ignition temperature (T _b) significantly, compared with red phosphorus (RP). The thermodynamic properties which include apparent activation energy (E ), pre‐exponential factor (A ), activation entropy (ΔS ^#), activation enthalpy (ΔH ^#) and Gibbs free energy (ΔG ^#) of RP and MRP are obtained. Moreover, the MRP can reduce the water absorption and friction sensitivity of red phosphorus smoke agent significantly with the best content of phenolic resin is 0.5 % or 1 %.     

Study on the Compatibility of Tetraethylammonium Decahydrodecaborate (BHN) with some Energetic Components and Inert Materials

The compatibility of tetraethylammonium decahydrodecaborate (BHN) with some energetic components and inert materials of solid propellants was studied by DSC method, where glycidyl azide polymer (GAP), cyclotrimethylenetrinitramine (RDX), cyclotetramethylenetetranitroamine (HMX), lead 3‐nitro‐1,2,4‐triazol‐5‐onate (NTO‐Pb), hexanitrohexaazaisowurtzitane (CL‐20), 3,4‐dinitrofurzanfuroxan (DNTF), N‐guanylurea‐dinitramide (GUDN), aluminum powder (Al, particle size=12.18 μm) and magnesium powder (Mg, particle size: 44–74 μm) were used as energetic components and polyoxytetramethylene‐co‐oxyethylene (PET), polyethylene glycol (PEG), addition product of hexamethylene diisocyanate and water (N‐100), hydroxyl terminated polybutadiene (HTPB), cupric adipate (AD‐Cu), cupric 2,4‐dihydroxy‐benzoate (β‐Cu), lead phthalate (ϕ‐Pb), carbon black (C. B.), aluminum oxide (Al₂O₃), 1,3‐dimethyl‐1,3‐diphenyl urea (C₂), di‐2‐ethylhexyl sebacate (DOS) and potassium perchlorate (KP), were used as inert materials. It was concluded that the binary systems of BHN with NTO‐Pb, CL‐20, aluminum powder, magnesium powder, PET, PEG, N‐100, AD‐Cu, β‐Cu, ϕ‐Pb, C. B., Al₂O₃, C₂, DOS, and KP are compatible, and systems of BHN with GAP and HMX are slightly sensitive, and with RDX, DNTF, and GUDN are incompatible. The impact and friction sensitivity data of BHN and BHN in combination with the energetic materials under present study were obtained, and there was no consequential affiliation between sensitivity and compatibility.     

Explosive Strength and Impact Sensitivity of Several PBXs Based on Attractive Cyclic Nitramines

Plastic explosives based on different cyclic nitramines with different polymeric matrices were prepared and studied. The used polymeric matrices were fabricated on the basis of polyisobutylene (PIB), acrylonitrile‐butadiene rubber (ABR), Viton A, and polydimethyl‐siloxane as binders, whereas the nitramines named RDX (1,3,5‐trinitroperhydro‐1,3,5‐triazine), β‐HMX (β‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine), BCHMX (cis‐1,3,4,6‐tetranitrooctahydroimidazo‐[4,5‐d]imidazole) and ε‐HNIW (ε‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane) were used as explosive fillers. Commercial Semtex 10, based on pentaerythritol tetranitrate (PETN), was used for comparison. Impact sensitivity, loading density, ρ, detonation velocity, D, and relative explosive strength (RS) measured by ballistic mortar were determined. It was concluded that plastic BCHMX based on Viton A or PIB‐matrix exhibits higher RS compared with PBXs based on RDX and HMX. Correlations between RS and the impact sensitivity, the ρD² term and the square of the detonation velocity were studied and discussed. The results confirm the well‐known fact that increasing the performance is usually accompanied by an increase in the sensitivity of the explosives. In this connection, Viton A enables achieving a high RS, but with a relatively high sensitivity of the PBXs, whereas the polydimethyl‐siloxane matrix should perhaps give PBXs with optimum explosive strength and sensitivity parameters.     

Sensitivity and Detonation Characteristics of Selected Nitramines Bonded by Sylgard Binder

Four plastic explosives based on cyclic nitramines and polymeric matrix were prepared and studied. The nitramines were RDX (1,3,5‐trinitro‐1,3,5‐triazinane), HMX (1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane), BCHMX (cis‐1,3,4,6‐tetranitro‐octahydroimidazo‐[4,5‐d]imidazole), and ϵ‐CL20 (ϵ‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane, ϵ‐HNIW). Sylgard 184 was used in the all PBXs prepared samples as a binder. The sensitivities to different mechanical stimuli were determined. The detonation velocities were experimentally measured. Detonation characteristics were calculated by EXPLO5 thermodynamic code. For comparison, standard plastic explosives, Composition C4, Semtex 10, and EPX‐1 were studied. Results showed that the experimental detonation velocities as well as the calculated detonation parameters decrease in the following order: CL20‐sylgard>HMX‐sylgard≥BCHMX‐sylgard>RDX‐sylgard. Calculations by EXPLO5 computer program resulted in detonation velocities close to the experimental ones with 3.1 % maximum difference. Urizar coefficient for the Sylgard binder was calculated from experimental data. An inverse linear relationship between friction sensitivity and heat of detonation of the studied samples was observed. Sylgard binder significantly decreased the sensitivity of all the studied nitramines. Among these prepared samples, the properties of BCHMX‐sylgard are similar to other ordinary plastic explosives.     

5‐Amino‐3,4‐dinitropyrazole as a Promising Energetic Material

The nitrogen‐rich energetic compound 5‐amino‐3,4‐dinitropyrazole (5‐ADP) was investigated using complementary experimental techniques. X‐ray diffraction indicates the strong intermolecular hydrogen bonding in 5‐ADP crystals. Compound exhibits low impact sensitivity (23 J) and insensitivity to friction. The activation energy of thermolysis determined to be 230±5 kJ mol⁻¹ from DSC measurements. Accelerating rate calorimetry indicates the lower thermal stability (173 °C) of 5‐ADP than that of RDX, which is probably the main concern about using this compound. 5‐ADP also exhibits good compatibility with common energetic materials (viz. TNT, RDX, ammonium perchlorate), including an active binder. The burning rate of 5‐ADP monopropellant is higher than that of benchmark HMX, while the pressure exponent 0.51±0.04 is surprisingly low. Addition of ammonium perchlorate does not affect the pressure exponent of 5‐ADP, while the burning rate increases. The 5‐amino‐3,4‐dinitropyrazole exhibits a notable combination of combustion performance, low sensitivity, and good compatibility, which renders it as a promising energetic material.     

Synthesis of Three Novel Laurylamine‐Derived Long‐Chain Alkyl Bonding Agents and Their Interactions with RDX

Three novel long‐chain alkyl bonding agents including 1,1′‐dodecylimino‐bis[3‐[bis(2‐hydroxyethyl)amino]‐2‐propanol (DHAP), 1‐acetyl‐5‐dodecyl‐octahydro‐1,5‐diazocine‐3,7‐diol (ADODD) and 1,3‐bis(dodecylimino)‐5,5‐dimethyl‐2,4‐imidazolidinedione (DDID) were synthesized by modification of laurylamine. Interaction energies between bonding agents and RDX were calculated and compared using the molecular dynamics method. Effects of coating by different bonding agents on characteristic absorption peaks of RDX were analyzed by micro‐infrared spectroscopy. The adhesion degrees of different bonding agents on the surface of RDX solid particles were calculated by XPS methods. The three prepared bonding agents were added to the HTPB/RDX/Al propellant and their effects on σ, ε_m, ε_b and Φ (the adhesion index between filling particles and binder matrix) value of propellant were studied. Simulation and experimental results showed that those three types of long‐chain alkyl bonding agents exhibit a strong interaction with RDX, with highest interaction potencial observed for DHAP, followed by DDID and ADODD. In addition, the current study demonstrated that results obtained by molecular dynamics simulation were in very good agreement with the experimental data.