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.     

Combustion Effects of Nitrofulleropyrrolidine on RDX‐CMDB Propellants

The effect of N‐methyl‐2‐(3‐nitrophenyl)pyrrolidino[3′,4′:1,2]fullerene (mNPF) on the decomposition characteristics of hexogen (RDX) was investigated using differential scanning calorimetry (DSC). The results show that mNPF can accelerate the decomposition of RDX, the peak temperature (T_p) of the exothermal decomposition is reduced by 6.4 K, and the corresponding apparent activation energy (E_a) is decreased by 8.7 kJ mol⁻¹. N‐methyl‐2‐(3‐nitrophenyl)pyrrolidino[3′,4′:1,2]fullerene (mNPF), carbon black (CB), and C₆₀ were used as combustion catalysts to improve the combustion performance of a composite modified double‐base propellant containing RDX (RDX‐CMDB). The burning rate experimental results show that mNPF has a stronger catalytic effect than C₆₀ and CB. The magnitude of the effect of the three carbon substances on the enhancement of the burning rate is as follows: mNPF>C₆₀>CB. The catalytic effects of different contents of mNPF on the burning rates of RDX‐CMDB propellants were also studied, and the results show that the burning rates of RDX‐CMDB propellants are improved with increasing mNPF content. The plateau burning rate of a RDX‐CMDB propellant can be increased to 19.6 mm s⁻¹ when 1.0 % mNPF is added, and the corresponding plateau combustion region occurs at 8–22 MPa.     

Application of Nitramines Coated with Nitrocellulose in Minimum Signature Isocyanate‐Cured Propellants

Cyclotrimethylenetrinitramine (RDX) coated with nitrocellulose (NC‐RDX) is prepared by an internal solution method and applied in a minimum signature isocyanate‐cured propellant. It was found that RDX was coated or bonded by NC to form NC‐RDX particles; the median particle diameter (d₅₀) and specific surface area of NC‐RDX are in the range from 150 to 240 μm and 0.03 to 0.04 m²⋅g⁻¹, respectively. The NC‐RDX particles could swell in nitrate ester plasticizers with relatively low swelling rate compared with NC added directly in the plasticizers. Different types of ballistic modifiers can be effectively added to NC‐RDX. It was experimentally shown that NC‐RDX can increase the content of NC in the propellant with viscosities in the range from 371 to 394 Pa s and improve the mechanical characteristics of the propellant with maximum tensile strength (σ_m) between 0.48 MPa<σ_m<1.92 MPa, elongation at maximum tensile strength (ε_m) between 28.0%<ε_m<37.3%, and elastic modulus between 3.18 MPa<E<8.68 MPa in the temperature range from −40 to +50 °C.     

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.     

Multiscale Simulation on the Influence of Dimethyl Hydantoin on Mechanical Properties of GAP/RDX Propellants

The influence of dimethyl hydantoin (DMH) on the mechanical properties of GAP/RDX propellant was studied by molecular dynamics (MD) and dissipative particle dynamics (DPD) simulation. The results showed that the binding energies (E_binding) between GAP and different surfaces of RDX were in the order of (010)>(001)>(100). Compared to GAP/RDX, GAP grafted with DMH (GAP‐DMH) exhibits higher binding energies with RDX, and the sequence of E_binding turns to (001)>(010)>(100). Radial distribution simulations demonstrated that GAP‐DMH is more close to the surfaces of RDX, increasing the van der Waals energies between GAP‐DMH and RDX. The stress and strain of GAP‐DMH/RDX excel those of GAP/RDX. DPD simulations showed that GAP‐DMH was able to restrain the agglomeration of RDX, to improve the dispersibility and to enlarge the contact surface with RDX, which also increased the mechanical properties of GAP/RDX propellant.     

Synthesis,Characterization, and Combustion Catalytic Activities of Copper(II) and Lead(II) Salts of p‐Nitrocalix[n]arenes (n=4, 6, 8)

Six copper(II) and lead(II) salts of p‐nitrocalix[n]arene (n=4, 6, 8) were synthsized and characterized. The DSC curves of all salts showed exothermic decomposition. Sensitivity studies revealed that all the salts with the exception of the lead salt of p‐nitrocalix[6]arene (NCPb6) are relatively insensitive materials. Investigations of the catalytic activities showed that most of the salts displayed high activities in thermal decomposition of NC‐NG and RDX. As evaluated in this work, the salts enhanced the burning rates of both double base (DB) and RDX‐component modified double base propellants. The best catalytic effect was obtained with NCPb6, which increased the burning rate of the DB propellant to the order of about 200 % (2–6 MPa) and 103–198 % (8–20 MPa) while decreasing the pressure index (n) to 0.22 (20–22 MPa).     

Study on the Synthesis and Interfacial Interaction Performance of Novel Dodecylamine‐Based Bonding Agents Used for Composite Solid Propellants

An effective pathway was explored to design and select proper bonding agents that could effectively improve the interfacial interactions between bonding agents and solid particles, with three novel synthesized alkyl bonding agents, dodecylamine‐N,N‐di‐2‐hydroxypropyl‐acetate (DIHPA), dodecylamine‐N,N‐di‐2‐hydroxypropyl‐hydroxy‐acetate (DIHPHA) and dodecylamine‐N,N‐di‐2‐hydroxypropyl‐cyano‐acetate (DIHPCA), as examples. Molecular dynamics simulation was applied to compare unit bond energies of these bonding agents with the [110] crystal face of ammonium perchlorate (AP) and the [120] crystal face of hexogen (RDX). The infrared test was used to characterize the interfacial interactions of these bonding agents with AP or RDX. XPS test was applied to calculate the adhesion percentage of the bonding agents on the surface of precoated AP or RDX particles. All of the above results indicated that these three bonding agents have strong interfacial interactions with AP or RDX in the order of DIHPCA>DIHPHA>DIHPA. The prepared three bonding agents were used in HTPB/AP/RDX/Al propellants, and their effects on tensile strength (σ), elongation under maximum tensile strength (ε_m), elongation at breaking point of the propellant (ε_b) and adhesion index (Φ) of the propellant were studied. The results show that the bonding agents improve the mechanical properties of the propellant in the order of DIHPCA>DIHPHA>DIHPA. The methods found from theoretical design, materials synthesis, and mechanistics studies up to practical application show effective guiding significance for choosing the proper bonding agent and improving the interfacial interactions between the solid particles and binder matrix.     

Applying modified hyperbranched polyester in hydroxyl‐terminated polyether/ammonium perchlorate/aluminium/cyclotrimethylenetrinitramine (HTPE/AP/Al/RDX) composite solid propellant

Composite solid propellants demand fine and stable mechanical properties, creep resistance and stress relaxation performance during their long storage and usage time. In this study, modified hyperbranched polyester (MHBPE) was prepared and introduced into HTPE/AP/Al/RDX (HTPE, hydroxyl‐terminated polyether; AP, ammonium perchlorate; RDX, cyclotrimethylenetrinitramine) solid propellant as an effective additive. The static tensile and dynamic mechanical properties of this propellant before and after the introduction of MHBPE were evaluated. The elevated interfacial interaction by using MHBPE between the binder and RDX fillers improved the toughness and elasticity of the propellant. The enhancement mechanisms were also confirmed by the influence on the fracture surface morphology of the binder which was investigated by SEM. In addition, some influence on the dynamic mechanical properties of HTPE/AP/Al/RDX propellant caused by MHBPE was investigated by dynamic mechanical analysis. The creep behaviors of the HTPE/AP/Al/RDX propellants with and without MHBPE were also investigated at different stresses and temperatures. Reduced creep strain rate and strain were obtained for the modified propellant, implying enhanced creep resistance performance. The creep properties were quantitatively evaluated using a six‐element model and the long‐term creep performance of the propellant was predicted using the time–temperature superposition principle. A creep behavior of nearly 10⁶ s at 30 °C could be acquired in a short‐term experiment (800 s) at 30–70 °C. Moreover, the stress relaxation investigation of the propellants with and without MHBPE at ?40 °C, 20 °C and 70 °C suggested that MHBPE/HTPE/AP/Al/RDX propellant possessed better response ability to deformation. Thus, the application of MHBPE provides an efficient route of reinforcement to enhance the creep resistance and stress relaxation properties. © 2020 Society of Chemical Industry     

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.     

Thermal Decomposition,Kinetics and Compatibility Studies of Poly(3‐difluoroaminomethyl‐3‐methyloxetane) (PDFAMO)

The thermal decomposition of poly(3‐difluoroaminomethyl‐3‐methyloxetane) (PDFAMO) with an average molecular weight of about 6000 was investigated using thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). The kinetics of thermolysis were studied by a model‐free method. The thermal decomposition of PDFAMO occurred in a two‐stage process. The first stage was mainly due to elimination of HF and had an activation energy of 110–120 kJ mol⁻¹. The second stage was due to degradation of the polymer chain. The Fourier transform infrared (FTIR) spectra of the degradation residues showed that the difluoroamino groups decomposed in a two‐step HF loss at different temperatures. The remaining monofluoroimino groups produced by the incomplete elimination of HF were responsible for the two‐stage thermolysis process. The compatibility of PDFAMO with some energetic components and inert materials used in polymer‐bonded explosives (PBXs) and solid propellants was studied by DSC. It was concluded that the binary systems of PDFAMO with cyclotrimethylenetrinitramine (RDX), 2,4,6‐trinitrotoluene (TNT), 2,4‐dinitroanisole (DNAN), pentaerythritol tetranitrate (PETN), ammonium perchlorate (AP), aluminum powder (Al), aluminum oxide (Al₂O₃) and 1,3‐diethyl‐1,3‐diphenyl urea (C₁) were compatible, whereas the systems of PDFAMO with lead carbonate (PbCO₃) and 2‐nitrodiphenylamine (NDPA) were slightly sensitized. The systems with cyclotetramethylenetetranitroamine (HMX), hexanitrohexaazaisowurtzitane (CL‐20), 3‐nitro‐1,2,4‐triazol‐5‐one (NTO), ammonium nitrate (AN), magnesium powder (Mg), boron powder (B), carbon black (C. B.), diphenylamine (DPA), and p‐nitro‐N‐methylamine (PNMA) were incompatible. The results of compatibility studies fully supported the suggested thermal decomposition mechanism of PDFAMO.     

HAN-基凝胶推进剂的热分解反应动力学

为研究 HAN‐基凝胶推进剂的热分解特性,利用差示扫描量热仪（DSC）和热重分析仪（TGA）对两种含不同质量聚乙烯醇（PVA ）的 HAN‐基凝胶推进剂样品进行热分析试验,并与一种双基推进剂进行对比。分析了HAN‐基凝胶推进剂和双基推进剂的热分解过程,得到热分解反应的动力学参数;采用等转化率法计算了活化能,采用Zhang‐Hu‐Xie‐Li等方法计算出热爆炸临界温度和自加速分解温度。采用Malek法推断出两种 HAN‐基凝胶推进剂样品的热分解反应的最可几机理函数。结果表明,HAN‐基凝胶推进剂的热分解是一个连续的放热过程,热分解较为彻底,残渣较少,活化能约为100 kJ／mol。当PVA含量增加时,其热爆炸临界温度和自加速分解温度升高。与双基推进剂相比,HAN‐基凝胶推进剂具有较好的热安定性。     

Studies on RDX Influence on Performance Increase of Triple Base Propellants

Conventional triple base propellants are currently used for high performance tank and field gun ammunition. The aim of the present study was to improve the chemical energy of the triple base propellant by partial replacement of picrite by RDX to achieve higher force constant (F) and lower specific heat ratio (γ). Details of theoretical and experimental studies carried out on six triple base propellant formulations are discussed in this paper. It can be concluded that partial replacement of picrite by RDX in the triple base propellant formulations achieved higher chemical energy as well as improved ballistic performance.     

Thermal Decomposition Research on 1,5‐Diazabicyclo[3.1.0] Hexane (DABH) as a Potential Low‐toxic Liquid Hypergolic Propellant

1,5‐Diazabicyclo[3.1.0] hexane (DABH) was found a potential hypergolic liquid propellant. The physical and energetic properties of DABH, 2‐(dimethylamino) ethyl azide (DMAZ), and monomethyl hydrazine (MMH) were compared. The ignition delay time of DABH with nitrogen tetroxide was 1 ms, which was shorter than DMAZ and similar with MMH. The toxicology experiment showed that half lethal dose (LD₅₀) of DABH was 621.0 mg kg⁻¹, which suggested that DABH was promising to be used as low‐toxic liquid propellant. Thermal decomposition experiments showed that the apparent activation energy (E ) was about 66.3 kJ mol⁻¹. The thermal decomposition calculated results from Madhusudanan‐Krishnan‐Ninan integration, Satava‐Sestak integration and Achar differential methods were compared and the pre‐exponential factor were obtained.     

撞击作用下螺压复合改性双基推进剂药片的响应

采用落锤仪研究了螺压复合改性双基(CMDB)推进剂药片在撞击作用下发生分解、燃烧或爆炸响应的临界值,获得了不同RDX含量、样品厚度及样品温度对推进剂在撞击作用下响应临界值的影响规律。结果表明,在推进剂中引入RDX不会增加推进剂对撞击刺激的敏感程度;RDX的质量分数为0~54.5%时,随着RDX含量的增加,推进剂药片对撞击刺激的敏感程度逐渐降低;样品厚度为1、2、3mm时,随着样品厚度的增加,推进剂药片对撞击刺激的敏感程度显著降低;推进剂在70℃时对撞击刺激比25℃时更加敏感。     

Kinetics of Nano Titanium Dioxide Catalyzed Thermal Decomposition of Ammonium Nitrate and Ammonium Nitrate‐Based Composite Solid Propellant

This study deals with the influence of nanosized titanium dioxide (TiO₂) catalysts on the decomposition kinetics of ammonium nitrate (AN) and ammonium nitrate‐based composite solid propellant. TiO₂ nanocatalyst with an average particle size of 10 nm was synthesized by sol‐gel method using titanium alkoxide as precursor. Formation of nanostructured TiO₂ and presence of its anatase and brookite phases was confirmed by powder X‐ray diffraction (PXRD) and selected area diffraction (SAED) studies. Nano TiO₂ was further characterized by transmission electron microscopy (TEM), infrared (IR) spectroscopy, and thermogravimetry. The catalytic effect of TiO₂ nanocatalysts on the solid state thermal decomposition reaction of AN and nonaluminized HTPB/AN propellant was evaluated. To ascertain the effectiveness of the TiO₂ nanocatalyst, the thermal kinetic constants for the catalytic and non‐catalytic decomposition of AN and AN propellant samples were computed by using a nonlinear integral isoconversional method. Catalytic influence was evident from the lowering of activation energy for the catalyzed decomposition reactions. Apparently, the nanocatalysts provide Lewis acid and/or active metal sites, facilitating the removal of AN dissociation products NH₃ and HNO₃ and thereby enhance the rate of decomposition. The changes in the critical temperature of thermal explosion of AN and AN propellant samples due to the addition of TiO₂ nanocatalyst were also computed and the possible reasons for the changes are discussed.     

Thermal decomposition of energetic thermoplastic elastomers of poly(glycidyl nitrate)

Energetic thermoplastic elastomers (ETPEs) are futuristic binders for propellant/explosive formulations. Poly(glycidyl nitrate) (PGN)‐based ETPEs have excellent performance, including a high energy and high oxygen content. PGN‐based ETPEs were synthesized on PGN as a soft segment and hexamethylene diisocyanate extended 1,4‐butanediol as a hard segment by a prepolymerization method. The thermal behavior of the PGN‐based ETPEs was investigated by thermogravimetric analysis (TGA) and derivative thermogravimetry. A fitting strategy was adopted to study every stage of decomposition. The results show that the ETPEs had four main decomposition processes, and the peaks of each stage were at 212, 262, 322, and 414°C. The gas products were tested by TGA/Fourier transform infrared spectroscopy/mass spectrometry, and the main gas products of the samples were N₂O, CH₂O, C₂H₄O, and CO₂. The previous results indicate the proposed mechanism of thermal decomposition. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40965.     

Surface Coating of RDX with a Composite of TNT and an Energetic‐Polymer and its Safety Investigation

To improve the safety of RDX (hexogen), an energetic polymer (HP‐1) was introduced to coat RDX with 2,4,6‐trinitrotoluene (TNT) by combining the solvent–nonsolvent and the aqueous suspension‐melting method. Scanning electron microscope (SEM), transmission electron microscope (TEM), and X‐ray photoelectron spectrometry (XPS) were employed to characterize the samples, and the role of HP‐1 in the coating process was discussed. The impact sensitivity, friction sensitivity, and the thermal stability of unprocessed and coated RDX were investigated, and the explosion heat of samples was also estimated. Results indicate that HP‐1 improves the wetting ability of the liquid coating material on RDX surface and reinforces the connection between RDX and the coating material. By surface coating, the impact and friction sensitivity of RDX decrease obviously; the drop height (H₅₀) is increased from 37.2 to 58.4 cm, and the friction probability is reduced from 92 to 38%. The activation energy (E) and the self‐ignition temperature increase by 10457.38 J⋅mol⁻¹ and 1.8 K, respectively. The explosion heat is reduced merely by 0.93%.     

含RDX高能太根发射药的热分解性能

运用TG和DSC方法,研究了RDX含量对太根发射药热分解性能的影响。结果表明：含RDX的高能太根发射药的热分解过程是分阶段完成的,第一阶段主要为硝酸酯的热分解,第二阶段主要为RDX的热分解。随着RDX含量增加,第一阶段放热量减少,第二阶段放热量增加。各阶段放热量和RDX含量成指数关系,热失重百分率与RDX含量成线性关系。试验结果为该发射药的应用提供了理论和实验基础。     

含黑索今酮的火药热分解及燃烧性能研究

用ＤＳＣ技术考察了７种含黑索今酮（Ｋｅｔｏ－ＲＤＸ）火药的热分解特性,并对其中３种进行了密闭爆发器测试。将ＤＳＣ数据对动力学方程进行拟合以求得动力学参数。从密闭爆发器测试结果转换得到了该３种火药的燃速－压力曲线,并对其进行了转折性分析。结果表明,向火药中加入Ｋｅｔｏ－ＲＤＸ可提高火药燃速并降低其热分解表观活化能。含Ｋｅｔｏ－ＲＤＸ的火药其燃速压力指数在低压区较在高压区为高。在火药中同时存在有Ｋｅｔｏ－ＲＤＸ和ＲＤＸ对火药热分解和燃烧的稳定性是不利的。仅由Ｋｅｔｏ－ＲＤＸ与双基粘结剂组成的火药,其燃速压力指数较由ＲＤＸ与双基粘结剂组成的火药为低。     

RDX基发射药相容性和安定性的研究

为了解由黑索今(RDX)、聚氨酯黏合剂、硝化棉等组分组成的发射药的相容性和安定性,采用差示扫描量热法(DSC)进行测定。根据不同加热速率下的峰温,进而求得加热速率趋于零时试样的峰温TP0、单独体系相对于混合体系分解峰温的改变量ΔTP及表观活化能改变率ΔE:Ea,考察了不同单独体系下的发射药的相容性和安定性。研究结果表明,以单基发射药作为单独体系,新型发射药的相容性较好;以RDX或聚氨酯作为单独体系,新型发射药的相容性均较差;新型发射药的安定性低于RDX,高于硝化棉。