Synthesis and Interfacial Adhesion Interaction of Borate Ester Bonding Agents Used for HTPB Propellants

The external monomers N‐methyl‐N,N‐diethanolamine, N‐butyl‐N,N‐diethanolamine, N‐(2‐cyanoethyl) diethanolamine, and N,N‐dihydroxyl‐3‐aminmethyl propionate were synthesized by modification of diethanolamine to evaluate the effects of external monomer molecular structure on the interfacial interactions of borate ester bonding agent (BEBA) applied in four‐component hydroxy‐terminated polybutadiene (HTPB) propellants. The compounds were characterized by IR and NMR spectroscopy. A series of BEBAs were synthesized using the as‐synthesized external monomers as well as diethanolamine. The interfacial interactions are evaluated using thermodynamic methods including acid‐base interaction enthalpy and wetting theory among the components in HTPB propellants. The experimental results indicate that the addition of BEBA‐3 prepared from N‐(2‐cyanoethyl) diethanolamine can significantly improve the interaction ethalpies and surface properties of the components in HTPB propellants. The results from the mechanical properties testing and SEM observations are in accordance with the results from the thermodynamic analysis of the interfacial adhesion interactions.     

Determination of Primary Amine Content in Bonding Agent Used in Composite Solid Propellants

The primary amine content in tetraethylenepentamine (TEPA) and TEPAN, a bonding agent used in composite solid propellants, was determined by near infrared (NIR) spectroscopy and the results were compared to those obtained by potentiometry. The band at 4930 cm⁻¹, which showed to be influenced only by primary amine groups, was chosen as the analytical band. The calibration curves based on isopropylamine (IPA) and isopropylamine/dibutylamine (IPA/DBA) mixtures proved to be suitable for determining the NH₂ content of TEPA or of samples containing mixtures of NH and NH₂ groups. It was found that TEPA contains 26.4 % of NH₂ and 25.7 % of NH, and that TEPAN contains 0.5 % of NH₂, confirming the low content of primary amine of this bonding agent. The lowest amine equivalent of TEPA is 31.1±0.3 g/eq, as determined by potentiometry, was found because this technique measures the total hydrogen content, including primary and secondary amines. The literature value of 62.6 g/eq for TEPA ACROS obtained by potentiometry in a non aqueous medium and related to the first inflection of the primary amine, validates the value obtained by NIR in this work for a similar type of amine. The equivalent weight obtained by NIR spectroscopy (62.7 g/eq) allowed to calculate the molar mass of TEPA of 195.6 g mol⁻¹, which is close to the typical value of 200 g mol⁻¹.     

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.     

Energetic Abilities of Solid Composite Propellants Based on 3,4,5-Trinitropyrazole and Ammonium Dinitramide

The investigation aims at the expansion of the basis of formulations of solid composite propellants by introducing new compositions with lower sensitivity to mechanic impact and improved thermal stability.The formulations based on trinitropyrazole(TNP)contains a binder(a hydrocarbon or active one),aluminum and inorganic oxidizer ADN.The results show that a binary formulation TNP+active binder(18%-19%)(volume fraction)with no metal is well designed which would achieve high specific impulse(at Pc∶Pa=40∶1)of 248s,high density of 1.80g/cm3 and combustion temperature Tcabout 3 450K.In terms of energy,metal-free compositions with TNP lose a bit to those with HMX,only if HMX fraction in formulation is higher than 45%-50%.     

Synthesis,Characterization and Thermal Properties of Poly(glycidyl azide‐r‐3‐azidotetrahydrofuran) as Azido Binder for Solid Rocket Propellants

Azido polymers have been investigated as energetic binders in the area of solid rocket propellants. However, the low temperature mechanical properties of them are not comparable with the traditional propellant binders. In this work, a new kind of azido binder named poly (glycidyl azide‐r‐3‐azidotetrahydrofuran) (PGAAT) was successfully synthesized. The molecular structures of monomers and copolymers were characterized. The sensitivity and thermal properties of the azido binder were studied. The cationic copolymerization of 3‐methylsulfonyloxytetrahydrofuran with ternary cyclic ethers was confirmed. The PGAAT azido binder exhibited attractive features like low glass transition temperature (T_g, −60 °C) and high energy (1798 J/g). The results indicate that the polymer is a suitable candidate binder for the solid rocket propellants.     

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.     

Effect of Pre‐strain Aging on the Damage Properties of Composite Solid Propellants based on a Constitutive Equation

Accelerated aging tests under pre‐strain were conducted on HTPB‐based composite solid propellant with the goal of investigating the effect of pre‐strain aging on its damage properties. A statistical damage constitutive model based on continuum damage theory and statistical strength theory was established. The aging damage coefficient, making aging process of propellant equivalent to a form of damage, was introduced to correct the damage variable. Experimental results show that theoretical model has good agreement with experimental results and can accurately describe the mechanical behavior of propellant during pre‐strain aging. Further analysis indicated that the damage effects caused by pre‐strain can be identified from the equation of the aging damage coefficient. Aging time influences both tensile strength and shape characteristics of the stress‐strain curve of propellant in the damage stage, while pre‐strain only decreased the tensile strength. The strain damage threshold value decreased linearly over the aging period and with increasing pre‐strain level during the aging process.     

Burning Characteristics of Ammonium Nitrate‐Based Composite Propellants Supplemented with Fe2O3

Ammonium nitrate (AN)‐based composite propellants have attracted a considerable amount of attention because of the clean burning nature of AN as an oxidizer. However, such propellants have several disadvantages such as poor ignition and a low burning rate. In this study, the burning characteristics of AN‐based propellants supplemented with Fe₂O₃ as a burning catalyst were investigated. The addition of Fe₂O₃ is known to improve the ignitability at low pressure. Fe₂O₃ addition also increases the burning rate, while the pressure exponent generally decreases. The increasing ratio (R) of the burning rate of the AN/Fe₂O₃ propellant to that of the corresponding AN propellant vs. the amount of Fe₂O₃ added (ξ) depends on the burning pressure and AN content. R decreases at threshold value of ξ. The most effective value of ξ for increasing the burning rate was found to be 4 % for the propellant at 80 % AN, and the value generally decreased with decreasing AN content. According to thermal decomposition kinetics, Fe₂O₃ accelerates the reactions of AN and binder decomposition gases in the condensed‐ and/or gas‐phase reaction zones. The burning characteristics of the AN‐based propellant were improved by combining catalysts with differing catalytic mechanisms instead of supplementing the propellant with a single catalyst owing to the multiplicative effect of the former.     

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 %.     

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.     

复合固体推进剂的催化热分解研究

用热分析技术研究复合固体推进剂凝聚相的催化热分解反应，得到大量的热分解参数和有关催化剂的作用规律。     

两种无机粒子填充聚合物复合材料界面黏结强度表征参数对比研究

界面黏结强度是影响无机粒子填充热塑性塑料力学性能的重要因素之一。引入界面相互作用参数和界面脱黏角两种无机粒子填充聚合物复合材料界面黏结强度参数,并以无机粒子填充聚丙烯复合材料为例,表征了无机粒子与聚合物界面的黏结强度,考察了两者之间的相关关系。结果表明,两种界面黏结强度表征参数呈明显线性负相关关系。     

Multi‐Parameter Study of Nanoscale TiO2 and CeO2 Additives in Composite AP/HTPB Solid Propellants

A statistical Taguchi L8 matrix was used to conduct a multi‐parameter study of the use of nanoscale additives in composite solid propellants. The additives studied were TiO₂ (titania) and CeO₂ (ceria). The other parameters involved in the experiment were the oxidizer loading and distribution, additive percentage and size, additive size (nano‐scale or μm‐scale), and the mixing method. Four baseline propellants without additives were also produced for comparison. The propellants were tested from 3.45 to 13.78 MPa in a strand bomb, and burning rate curves were determined for all formulas. By analyzing the Taguchi matrix, the sensitivity of each parameter according to the pressure sensitivity and burning rate of the propellant was calculated. The dominant factors depend on whether the additive is needed for modifying the pressure index or the absolute value of the burning rate. In general, the effectiveness of the additives was most influenced by oxidizer percentage, oxidizer size distribution, and additive type. The amount of additive, mixing method, and additive size all had relatively minor impacts on the effectiveness of the additives.     

Estimation of the Ballistic Effectiveness of 3,4-and 3,5-Dinitro-1-(trinitromethyl)-1H-Pyrazoles as Oxidizers for Composite Solid Propellants

The experimental values of the enthalpy of formation of two isomeric 3,4-and 3,5-dinitro-1-(trinitromethyl)-1H-pyrazoles have been obtained(261.5±5.0and 246.4±6.7kJ/mol for crystalline 3,4-and 3,5-dinitro-1-(trinitromethyl)-1H-pyrazoles,respectively).The ballistic effectiveness of these potential oxidizers in composite solid propellants was studied.It is shown that these two oxidizers may be successfully applied in metal-free compositions or with a small content of metal.For the bottom stage 3,4-dinitro-1-(trinitromethyl)-1H-pyrazole is a bit better than 3,5-dinitro-1-(trinitromethyl)-1H-pyrazole,for the upper stage the both oxidizers show the equal ballistic parameters.These oxidizers allow to create metal-free solid composite propellants with the binder percentage not lower than 19%(volume fraction),with I3spequal to 256.5-257.0sat density equal to 1.72-1.74g/cm~3.     

Measurement and Analysis of the Burning Rate of HAN‐Based Liquid Propellants

A new device for measuring the linear burning rate of liquid propellants at high pressures is reported. High‐pressure environments were generated by the combustion of solid propellants. The coated propellants, which burn progressively, were introduced to maintain the approximate constant‐pressure environments. By use of ion probe transducers, measurements were made of the spread velocity of the flame surface, i.e. the apparent linear burning rate of the HAN‐based liquid propellant LP1846 (HAN =hydroxylammonium nitrate) was measured quantitatively at pressures from 6 to 28 MPa. The results show that it follows the exponential burning rate law. The burning rate coefficient and exponent were fitted by least‐squares methods. Based on the experiment, a simplified model of the linear burning rate of HAN‐based liquid propellants at high pressures was developed. The numerical simulation is found to be in good agreement with the experimental data.     

Study on the Viscoelastic Poisson‘s Ratio of Solid Propellants Using Digital Image Correlation Method

Digital image correlation methods were used for further studies of the viscoelastic Poisson's ratio of solid propellants. The Poisson's ratio and the Young's relaxation modulus of solid propellants were separately determined in a single stress relaxation test. In addition, the effects of temperature, longitudinal strain, preload and storage time on the Poisson's ratio of solid propellants were discussed. The Poisson's ratio master curve and the Young's relaxation modulus master curve were constructed based on the time‐temperature equivalence principle. The obtained results showed that the Poisson's ratio of solid propellants is a monotone non‐decreasing function of time, the instantaneous Poisson's ratio increased from 0.3899 to 0.4858 and the time of the equilibrium Poisson's ratio occurred late when the temperature was varied from −30 °C to 70 °C. The Poisson's ratio increased with temperature and longitudinal strain, decreased with preload and storage time, while the amplitude Poisson's ratio increased with preload, decreases with longitudinal strain and storage time. The time of the equilibrium Poisson's ratio occurred in advance with the increase of longitudinal strain, preload and storage time.     

Effects of an Organic‐inorganic Nanocomposite Additive on the Combustion and Erosion Performance of High Energy Propellants Containing RDX

A nanocomposite microsphere consisting of solid paraffin, nano‐TiO₂, nano‐BN, zeolitic imidazolate framework‐67 particles and polymethyl methacrylate was prepared and applied as a functional additive for high energy propellants (with about 23 wt % RDX) to reduce the barrel erosion and improve its combustion performance as well. High energy propellants modified with the nanocomposite were manufactured by a solvent extrusion technique. According to the scanning electron microscope and differential scanning calorimetry results, there exists a good compatibility between the nanocomposite and propellant matrix. The energy and combustion performance as well as erosion of the modified propellants were studied by a closed bomb test and an erosion tube device, respectively. Results showed that compared with the unmodified propellant, both the erosion and energy performance of modified high energy propellant gradually decreased with the increase of nanocomposites contents. When the content of nanocomposites was 5.1 %, the erosion mass of the modified propellant reduced to 37.0 % while the propellant force only decreased 5.7 %, indicating that the nanocomposite has enormous ability to improve gun erosion resistance while barely affect energy performance of propellant. Furthermore, the closed bomb burning curves of the samples showed that addition of nanocomposites to propellant matrix could prolong the combustion time, efficiently inhibit the initial generation rate of combustion gas, and further achieve the progressive burning of the propellants.     

Effects of Different Metal Fuels on the Characteristics for HTPB‐based Fuel Rich Solid Propellants

The microstructures and granularity distribution of different metal particles were investigated and the energy, sensitivity, and combustion properties of fuel rich solid propellants with different metal particles were studied in detail. It was found that the magnesium particles are more uniform than other metal powders, the mean diameter of the magnesium particles d₅₀=67.6 μm is much higher than those of the other ones, which are in the range of 7.1 μm<d₅₀<20.5 μm. Additionally, the preparation process of the Mg‐based propellant is easier than those of the other ones. The experimental results showed that the propellant containing magnesium powder was less sensitive to friction and impact (165.1 NM and 21.9 NM, respectively), whereas, the burning rates of propellants with Zr and ZrH₂ particles increased, and the pressure exponents decreased.     

Effects of Twin‐Screw Extrusion Processing on the Burning Rate of Composite Propellants

A new process for continuous manufacturing of composite propellants has been developed using Twin Screw Extrusion (TSE). The effects of TSE‐processing on the burning rates of an ammonium perchlorate (AP)‐based composite propellant have been characterized over a wide composition range (79 to 87 wt. % AP) and a wide range of screw speeds (45 to 85 RPM) using a quadratic model for an experimental Response Surface Analysis (RSA) based on the Kowalski, Cornell, and Vining (KCV) algorithm. Using Student‘s T‐test, it was determined that burning rates obtained from strand‐burning rate tests at 3.5 MPa, 7.0 MPa, and 10.5 MPa are affected only by the individual ingredients, the interaction between the coarse AP particles and the binder, and the screw speed. Measured burning rates were found to be 40% to 100% higher than Petite Ensemble Model (PEM) predictions, which was accounted for by modifying the PEM through a power law relationship with pressure that includes a rule‐of‐mixtures dependence of the exponent and coefficient on the weight fraction of coarse and fine AP particles. The resulting modified PEM reduced differences between the predictions and experimental data by 79% at 3.5 MPa, 83% at 7.0 MPa, and 78% at 10.5 MPa.     

A Novel Model for Predicting the Dense Phase Behavior of 3D Gas‐Solid Fluidized Beds

A novel phenomenological discrete bubble model was developed and tested for prediction of the hydrodynamic behavior of the dense phase of a 3D gas‐solid cylindrical fluidized bed. The mirror image technique was applied to take into account the effects of the bed wall. The simulation results were validated against experimental data reported in the literature that were obtained by positron emission particle tracking. The time‐averaged velocity profiles of particles predicted by the developed model were found to agree well with experimental data. The initial bubble diameter had no significant influence on the time‐averaged circulating pattern of solids in the bed. The model predictions clearly indicate that the developed model can fairly predict the hydrodynamic behavior of the dense phase of 3D gas‐solid cylindrical fluidized beds.