Neutral Polymeric Bonding Agents (NPBA) and Their Use in Smokeless Composite Rocket Propellants Based on HMX‐GAP‐BuNENA

Very few efficient bonding agents for use in solid rocket propellants with nitramine filler materials and energetic binder systems are currently available. In this work, we report the synthesis, detailed characterization, and use of neutral polymeric bonding agents (NPBA) in isocyanate‐cured and smokeless composite rocket propellants based on the nitramine octogen (HMX), the energetic binder glycidyl azide polymer (GAP), and the energetic plasticizer N‐butyl‐2‐nitratoethylnitramine (BuNENA). These polymeric bonding agents clearly influenced the viscosity of the uncured propellant mixtures and provided significantly enhanced mechanical properties to the cured propellants, even at low NPBA concentrations (down to 0.001 wt‐% of propellant). A modified NPBA more or less free of hydroxyl functionalities for interactions with isocyanate curing agent provided the same level of mechanical improvement as regular NPBA containing a substantial number of reactive hydroxyl groups. However, some degree of reactivity towards isocyanate is essential for function.     

The Mechanism of Filler Reinforcement from addition of neutral polymeric bonding agents to energetic polar propellants

It has been demonstrated that addition of small amounts of the newly developed neutral polymeric bonding agents (NPBA's) to energetic propellants such as HMX/PEG/NG composites causes strong filler reinforcement. The mechanism of this reinforcement occurs through interfacial effects, and not because of an overall increase in the crosslink density of the binder. It has been demonstrated directly that the NPBA's have a favorable relative affinity for HMX and concentrate at the solid surface during mixing. All the experimental evidence supports the theory that highly crosslinked polymeric shells form around the HMX particles and chemically bond to the binder matrix during the cure, thus causing an increase in the initial modulus. Furthermore, these shells appear to eliminate the weak, soft layers around the particles, and hence filler reinforcement persists up to much higher elongation than without addition of NPBA. Based on the filler reinforcement observed, the simple one-step procedure of incorporating our NPBA is almost as effective as the more costly process of precoating the particles.     

键合剂对硝酸酯增塑BAMO-THF推进剂力学性能的影响

采用单向拉伸试验研究了2类键合剂对硝酸酯增塑BAMO-THF推进剂力学性能的影响,并用扫描电镜观察了不含键合剂和含有中性聚合物键合剂(NPBA)的硝酸酯增塑BAMO-THF推进剂切面微观形貌。结果表明,相比于MAPO、T-313、HX-752极性键合剂,中性键合剂使硝酸酯增塑BAMO-THF推进剂的最大抗拉强度和最大断裂伸长率明显提高;当4#NPBA的质量分数为0.15%时,推进剂最大抗拉强度和最大断裂伸长率均达到最大。     

Isocyanate‐Free and Dual Curing of Smokeless Composite Rocket Propellants

Traditional composite rocket propellants are cured by treatment of hydroxyl‐terminated prepolymers with polyfunctional aliphatic isocyanates. For development of smokeless composite propellants containing nitramines and/or ammonium dinitramide (ADN), energetic binder systems using glycidyl azide polymer (GAP) are of particular interest. Polyfunctional alkynes are potential isocyanate‐free curing agents for GAP through thermal azide‐alkyne cycloaddition and subsequent formation of triazole crosslinkages. Propargyl succinate or closely related aliphatic derivatives have previously been reported for such isocyanate‐free curing of GAP. Herein, we present the synthesis and use of a new aromatic alkyne curing agent, the crystalline solid bisphenol A bis(propargyl ether) (BABE), as isocyanate‐free curing agent in smokeless propellants based on GAP, using either octogen (HMX) and/or prilled ADN as energetic filler materials. Thermal and mechanical properties, impact and friction sensitivity and ballistic characteristics were evaluated for these alkyne cured propellants. Improved mechanical properties could be obtained by combining isocyanate and alkyne curing agents (dual curing), a combination that imparted better mechanical properties in the cured propellants than either curing system did individually. The addition of a neutral polymeric bonding agent (NPBA) for improvement of binder‐filler interactions was also investigated using tensile testing and dynamic mechanical analysis (DMA). It was verified that the presence of isocyanates is essential for the NPBA to improve the mechanical properties of the propellants, further strengthening the attractiveness of dual cure systems.     

硝胺类推进剂用键合剂的研究进展

综述了各类适用于硝胺类推进剂的键合剂的研究情况,认为中性聚合物键合剂（NPBA）提高硝胺类推进剂的力学性能效果较好,需根据具体配方情况合成具有适当溶度积参数的NPBA,并根据NPBA的临界温度确定合适的推进剂制备温度条件。酰胺类和硼化物类键合剂具有成为优良键合剂的潜力,应加强对其合成与应用的研究。通过文献分析,认为键合剂的作用效果是官能团因素和分子结构因素共同作用的结果。对今后用于硝胺类推进剂的键合剂的发展提出了一些建议。     

Improvement of Mechanical Properties of Plastic Bonded Explosive Using Neutral Polymeric Bonding Agent

The technical objective of this investigation is to examine the processability and achievement of high tensile strength of AFX-231 through the use of NPBA as a replacement for nitrocellulose as a bonding agent. This study is centered on the formulation in which HMX solid particles are dispersed in the binder matrix containing highly polar plasticizer such as DEGDN, BTTN and PGA. When nitrocellulose of AFX-231 was replaced by NPBA as a bonding agent, a significant increase in the initial modulus and the stress were observed, while impact and friction sensitivities showed no differences. This observation indicates the hard shell formation around the particles. Among the modified formulations, Mod-24 showed less impact and friction sensitivities and higher initial modulus and maximum stress.     

Mechanical Properties of Smokeless Composite Rocket Propellants Based on Prilled Ammonium Dinitramide

Ammonium dinitramide (ADN) is a high performance solid oxidizer of interest for use in high impulse and smokeless composite rocket propellant formulations. While rocket propellants based on ADN may be both efficient, clean burning, and environmentally benign, ADN suffers from several notable disadvantages such as pronounced hygroscopicity, significant impact and friction sensitivity, moderate thermal instability, and numerous compatibility issues. Prilled ADN is now a commercially available and convenient product that addresses some of these disadvantages by lowering the specific surface area and thereby improving handling, processing, and stability. In this work, we report the preparation, friction and impact sensitivity and mechanical properties of several smokeless propellant formulations based on prilled ADN and isocyanate cured and plasticized glycidyl azide polymer (GAP) or polycaprolactone‐polyether. We found such propellants to have very poor mechanical properties in unmodified form and to display somewhat unreliable curing. However, by incorporation of octogen (HMX) and a neutral polymeric bonding agent (NPBA), the mechanical properties of such smokeless formulations were significantly improved. Impact and friction sensitivities of these propellants compare satisfactorily with conventional propellants based on ammonium perchlorate (AP) and inert binder systems.     

高能氧化剂改性研究进展

高能氧化剂的改性是降低其机械感度的一种重要方法。对推进剂中的氧化剂进行改性,不仅可以降低单组分的机械感度,也能提高推进剂的力学性能和改善推进剂的工艺性能。综述了高能固体氧化剂CL-20、ADN、HNF、HMX、RDX的改性研究进展。     

Microencapsulation of ADN with HTPB-based membrane in the presence of the bonding agents Tepan or Tepanol**

Ammonium dinitramide (ADN) has appeared as a promising oxidizer for green propellants and thereby a potential substitute for ammonium perchlorate, largely in use in composite propellants for tactical and strategic long-range missiles. The novelty lies in replacing ammonium perchlorate with a chlorine-free oxidizer less harmful to the health and environment. However, ADN is hygroscopic and can potentially react with other chemical components, which could be overcome by microencapsulating the particles. The simple coacervation method was tested herein to microencapsulate ADN with a membrane made of hydroxyl-terminated polybutadiene as pre-polymer and methylene diphenyl diisocyanate as the curing agent. The effect of polyamine bonding agents on the capsule formation was tested by adding 0.5 or 2 % of Tepan or Tepanol, whose efficacy to bond to ADN was confirmed by detecting ammonia release through infrared spectroscopy. The capsule membrane was examined by optical and scanning electron microscopy. The dissolution time and rate were the parameters adopted to quantify permeability in a straight dissolution test in water, which demonstrated that 0.5 % Tepanol can provide the most effective protection. The infrared spectroscopy indicated that 60 °C temperature for prolonged periods, normally experienced by propellants, does not chemically affect the capsules’ membrane but can turn it lumpy. In conclusion, these polyamine bonding agents can assist the capsule formation over ADN particles using the simple coacervation method, however, their functionality on mechanical properties of propellants needs to be substantiated in forthcoming works as well as the effect of the concentration of bonding agents on propellant formulations.     

Rocket Propellants with Reduced Smoke and High Burning Rates

Rocket propellants with reduced smoke and high burning rates recommend themselves for use in a rocket motor for high accelerating tactical missiles. They serve for an improved camouflage on the battle field and may enable guidance control due to the higher transmission of their rocket plume compared to traditional aluminized composite propellants. In this contribution the material based ranges of performance and properties of three non aluminized rocket propellants will be introduced and compared to each other. The selected formulations based on AP/HTPB; AP/PU/TMETN and AP/HMX/GAP/TMETN have roughly the same specific impulse of I_SP = 2430 Ns/kg at 70:1 expansion ratio. The burning rates in the pressure range from 10–18 MPa vary from to 26–33 mm/s for the AP/HTPB propellant, 52–68 mm/s for the formulation based on AP/PU/TMETN and 28–39 mm/s for the propellant based on AP/HMX/GAP. With 58% and 20% AP-contents the propellants with nitrate ester plasticizers create a much smaller secondary signature than the AP/HTPB representative containing 86% AP. Their disadvantage, however, is the connection of high performance to a high level of energetic plasticizer. For this reason, the very fast burning propellant based on AP/PU/TMETN is endowed with a low elastic modulus and is limited to a grain configuration which isn't exposed too much to the fast and turbulent airstream. The mechanical properties of the AP/HMX/GAP-propellant are as good or better as those of the AP/HTPB propellant. The first one exhibits the same performance and burn rates as the composite representative but produces only one fifth of HCl exhaust. For this reason it is recommended for missile applications, which must have high accelerating power together with a significantly reduced plume signature and smoke production.     

少烟NEPE推进剂的表面和界面性能

根据表面和界面化学原理,应用动态接触角测量仪和表面-界而张力仪测试了少烟NEPE推进剂的黏合剂体系(PNT)、填料(HMX、AP和Al粉)和键合剂的表面和界面性能.结果表明,填料(HMX、AP和Al粉)与黏合剂体系(PNT)的界面张力(γsl)大小顺序为:γAl/PNT＜γAP/PNT＜γHMX/PNT,填料与黏合剂体系的黏附功(Wa)大小顺序为:Wa(Al/PNT)＞Wa(HMX/PNT)＞Wa(AP/PNT);键合剂能够自发吸附和分散在推进剂的填料(HMX、AP和Al粉)表面和黏合剂体系中;在推进剂制备过程中,键合剂吸附于填料表面形成的界面能够稳定保持在黏合剂体系中;键合剂能明显提高推进剂的强度和模量,改善填料颗粒与黏合剂体系的界面粘结性能,这与表面性能测试结果一致.     

Influence of Particle Size and Mixing Technology on Combustion of HMX/Al Compositions

In this work, two widely used components of high‐energy condensed systems – HMX and aluminium – were studied. Morphology, thermal behaviour, chemical purity and combustion parameters of HMX as a monopropellant and Al/HMX as a binary system were investigated using particles of different sizes. It was shown that in spite of the differences in composition and particle size, combustion velocities are almost identical for micrometer‐sized HMX (m‐HMX) and ultrafine HMX (u‐HMX) monopropellants under pressure from 2 to 10 MPa. Replacement of the micrometer‐sized aluminium with ultrafine one in the system with m‐HMX leads to a burning rate increase by a factor of 2.5 and the combustion completeness raise by a factor of 4. Two mixing techniques to prepare binary Al/HMX compositions were applied: conventional and ‘wet’ technique with ultrasonic processing in liquid. Applying wet mixing results in a burning rate increase of 18% compared to the conventional mixing for systems with ultrafine metal. The influence of the component's particle size and the composition microstructure on the burning rate of energetic systems is discussed and analysed.     

Combustion of HMX-CMDB Propellants (II)

The burning rate characteristics of HMX-CMDB propellants were examined as a function of HMX concentration. In the region of low HMX concentration, below about 50%, the burning rate decreases with increasing the HMX concentration. However, in the region of high HMX concentration, above about 50%, the burning rate increases with increasing the HMX concentration. When the measured results are extrapolated to the 100% HMX concentration, it is recognized that the burning rate approaches the burning rate of an HMX single crystal. The burning rate analysis indicates that the effect of the addition of HMX particles within double-base propellants on burning rate is determined by the reaction rates in the gas phase and in the condensed phase. The gas phase reaction rate in the fizz zone decreases monotonously as the HMX concentration increases. On the other hand, the heat of reaction at the burning surface increases as the HMX concentration increases. The experimental results indicate that the burning rate with low HMX concentration is mainly controlled by the gas phase reaction rate and the burning rate with high HMX concentration is mainly controlled by the condensed phase reaction rate.     

Solvent effect on particle morphology in recrystallization of HMX (cyclotetramethylenetetranitramine) using supercritical carbon dioxide as antisolvent

Supercritical fluid processes have gained great attention as a new and environmentally benign method of preparing the microparticles of energetic materials like explosives and propellants. In this work, HMX (cyclotetramethylenetetranitramine) was selected as a target explosive. The microparticle formation of HMX using supercritical antisolvent (SAS) recrystallization process was performed and the effect of organic solvent on the size and morphology of prepared particles was observed. The organic solvents used in this work were dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), cyclohexanone, acetone, and N-methyl pyrrolidone (NMP).     

The properties of 1,3,3,5,7,7-hexanitro-1,5-diazacyclooctane (HCO) and its application in propellants

The properties of HCO and its application as a monopropellant were described. In comparison with HMX, it is also a high energetic explosive with high thermostability and can be used as an oxidizer in solid rocket propellants. Theoretical specific impulse of HCO-double base propellant systems were calculated and the burning rates and thermostability of propellant were experimentally determined. Propellants were prepared with a spray-casting process. As an oxidizer in solid rocket propellant, HCO shows better characteristics under certain aspects compared with HMX.     

Bioinspired Fabrication of Insensitive HMX Particles with Polydopamine Coating

The development of a facile method for large scale production of insensitive HMX particles is of great importance for energetic materials, especially for insensitive munitions. Inspired by mussels, HMX particles with a thin, robust, wettable and uniform coating based on the self‐polymerization of dopamine were prepared by one‐step solution stirring processes in the study. The as‐prepared HMX@PDA particles showed stable shape, size, and polymorphy compared with original HMX particles. With PDA (polydopamine) coating, the HMX@PDA particles exhibited better wettability, which could improve the adhesive properties between particles and other liquid components in a PBX (plastic bonded explosive). Furthermore, the mechanical sensitivities were decreased for the HMX@PDA particles because of the uniform and smooth PDA coating decreasing the hot spots on the surface of the HMX particles. HMX@PDA particles produced by a facile scalable process might provide a promising substitute for sensitive HMX particles to enhance the safety and adhesive properties when used in PBX.     

Smokeless GAP‐RDX Composite Rocket Propellants Containing Diaminodinitroethylene (FOX‐7)

Composite rocket propellants prepared from nitramine fillers (RDX or HMX), glycidyl azide polymer (GAP) binder and energetic plasticizers are potential substitutes for smokeless double‐base propellants in some rocket motors. In this work, we report GAP‐RDX propellants, wherein the nitramine filler has been partly or wholly replaced by 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7). These smokeless propellants, containing 60% energetic solids and 15% N‐butyl‐2‐nitratoethylnitramine (BuNENA) energetic plasticizer, exhibited markedly reduced shock sensitivity with increasing content of FOX‐7. Conversely, addition of FOX‐7 reduced the thermochemical performance of the propellants, and samples without nitramine underwent unsteady combustion at lower pressures (no burn rate catalyst was added). The mechanical characteristics were quite modest for all propellant samples, and binder‐filler interactions improved slightly with increasing content of FOX‐7. Overall, FOX‐7 remains an attractive, but less than ideal, substitute for nitramines in smokeless GAP propellants.     

Theoretical Prediction of Physicochemical Properties,Performances and Sensitivities of some New Derivatives of Dinitro Triazolyl Triazine

In this paper, important properties of some new derivatives of dinitro triazolyl triazine as novel heterocyclic energetic compounds are evaluated and discussed by using some reliable models. The predicted properties are also compared with octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) as a benchmark compound and 2,4,6‐trinitro‐1,3,5‐triazine (TNTA) as a theoretically new high performance energetic compound. It is shown that some of these compounds can be seen as interesting high‐nitrogen organic explosives with relatively low sensitivity which could be introduced for some important industrial applications. Since some of the new compounds have good oxygen balance, calculated specific impulses confirm that these compounds can be considered as suitable oxidizers in solid propellants.     

Burning Rate – Pressure Relationship of NG‐PE‐PCP‐based High Energy Propellants

Nitramines are known to produce lower burning rates and higher pressure exponent (η) values. Studies on the burning rate and combustion behavior of advanced high‐energy NG/PE‐PCP/HMX/AP/Al based solid propellant processed by slurry cast route were carried out using varying percentages of HMX and AP. It was observed that propellant compositions containing only AP and Al loaded (total solids 75 %) in NG plasticized PE‐PCP binder produce comparatively lower pressure exponent (η) values similar to AP‐Al filled HTPB based composite propellants. However, energetic propellants containing high level of nitramine (40–60 %) produce high pressure exponent (0.8–0.9) values in the same pressure range. Incorporation of fine particle size AP (ca. 6 μm) and change in its concentration in the propellant composition reduces η value marginally and influences the burning rate. However, such compositions have higher friction sensitivity.     

Effect of Bonding Agent on the Mechanical Properties of GAP High‐Energy Propellant

Three kinds of bonding agent were chosen to improve the mechanical properties of GAP high‐energy composite propellant based on GAP, BuNENA, HMX, AP, and Al. These bonding agents are N,N ′‐bis(2‐hydroxyethyl) dimethylhydantoin and 1,3,5‐trisubstituted isocyanurates (BA1), cyano‐hydroxylated amines (BA2), and hyperbranched polyether with terminal groups substituted by hydroxyl, cyano and ester functional groups (BA3). To study the interaction between bonding agents and oxidizers, the effect of coating by bonding agents on the characteristic absorption peaks of AP and HMX were first studied by infrared spectroscopy. Then the effect of bonding agents on the adhesion work between oxidizers and binder system were determined. The results showed that BA2 has the strongest interaction with AP, whereas BA1 and BA3 have relatively strong interaction with HMX. The AP grain coated by BA2 has the strongest adhesion work to the binder system, and there is not much difference in the values of adhesion work towards binder system of three coated HMX grains. At last the three bonding agents were added to GAP propellant, which has a theoretical specific impulse of 276.03 s. When the three kinds of bonding agent was used alone, the sense of “dewetting” in propellant was relieved but still existed. The combination of BA2 to BA1 or BA3 improved the adhesions between oxidizers and binder system effectively, and the mechanical properties of GAP propellant reached to δ _m=0.69 MPa, ϵ _b=32.7 %.