An Advanced GAP/AN/TAGN Propellant. Part I: Ballistic Properties

A solid rocket propellant based on glycidyl azide polymer (GAP) binder plasticized with nitrate esters and oxidized with a mixture of ammonium nitrate (AN) and triaminoguanidine nitrate (TAGN) was formulated and characterized. Non‐lead ballistic modifiers were also included in order to obtain a propellant with non‐acidic and non‐toxic exhaust. This propellant was found to exhibit a burning rate approximately twice that of standard GAP/AN propellants. The exponent of the propellant is high compared to commonly used composite propellants but is still in the useable range at pressures below 13.8 MPa. This propellant may present a good compromise for applications requiring intermediate burn rate and impulse combined with low‐smoke and non‐toxic exhaust.     

Burning Characteristics of Ammonium Nitrate‐based Composite Propellants Supplemented with Ammonium Dichromate

Ammonium nitrate (AN)‐based composite propellants have attracted much attention, primarily because of the clean burning nature of AN as an oxidizer. However, such propellants have some disadvantages such as poor ignition and low burning rate. Ammonium dichromate (ADC) is used as a burning catalyst for AN‐based propellants; however, the effect of ADC on the burning characteristics has yet to be sufficiently delineated. The burning characteristics of AN/ADC propellants prepared with various contents of AN and ADC have been investigated in this study. The theoretical performance of an AN‐based propellant is improved by the addition of ADC. The increase in the burning rate is enhanced and the pressure deflagration limit (PDL) becomes lower with increasing amount of ADC added. The increasing ratio of the burning rate with respect to the amount of ADC is independent of the AN content and the combustion pressure. The optimal amount of ADC for improving the burning characteristics has been determined.     

Studies on Energetic Compounds Part 27: Kinetics and Mechanism of Thermolysis of Bis(Ethylenediamine)Metal Nitrates and Their Role in the Burning Rate of Solid Propellants

Four bis(ethylenediamine)metal(II) nitrate (BEMN) complexes, i.e. [M(EDA)₂](NO₃)₂, where M=Cu, Co, Ni and Zn, have been prepared and characterized. Thermolysis of these complexes induced by heat and drop‐weight impact has been investigated by TG‐DTG, DTA, explosion delay (D_E), explosion temperature (T_E) and impact sensitivity measurement. The kinetics of early thermolysis reaction prior to fast decomposition have been evaluated. Contracting area (CA, n=2) and contracting cube (CC, n=3) equations were found to give the best fits in isothermal TG data among all tested nine mechanism‐based kinetic models. The values of activation energy (E_a), T_E, D_E and activation energy for explosion (E*) have been found to be quite lower for the copper complex as compared to cobalt, nickel and zinc complexes. A mechanism of thermolysis has also been proposed. All these complexes were found to be insensitive towards impact of 2 kg weight up to the height of 110 cm. These complexes were used as energetic burning rate modifiers in the combustion of hydroxy‐terminated polybutadiene (HTPB)‐ammonium perchlorate (AP) composite solid propellants. A two‐fold increase in burning rate was observed with copper and cobalt complexes at low concentration (2% by wt.). The in situ freshly formed metal oxides with large number of active sites in their crystallites seem to be better additives for combustion of propellants.     

Insensitive munitions (IM) and combustion characteristics of GAP/AN composite propellants

Sensitivities to the ballistic shock and burn rate characteristics of GAP/AN composite propellants were investigated. Nitrate esters, such as TMETN and NC, were very effective ballistic modifier that provided useable burn rate and pressure rate exponent for minimum signature propellant based on AN. Their low temperature mechanical properties became less sensitive to the temperatures with nitrate esters. Dioctyl adipate platicized propellant showed excellent mechanical properties at operational temperature ranges. The primary initiation mechanism of card gap test was not dominated by the mechanical properties. Although NC significantly increased the critical shock pressure, 14.8% HMX and AP were less effective to the sensitivities. GAP/AN propellants showed excellent IM characteristics to the ballistic shock applied here.     

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.     

Burning Characteristics and Thermochemical Behavior of AP/HTPB Composite Propellant Using Coarse and Fine AP Particles

The burning rate of AP/HTPB composite propellant increases with increasing AP content and with decreasing AP size. In addition, the burning rate can be enhanced with the addition of Fe₂O₃. The burning characteristics and thermal decomposition behavior of AP/HTPB composite propellant using coarse and fine AP particles with and without Fe₂O₃ at various AP contents were investigated to obtain an exhaustive set of data. As the AP content decreased, the burning rate decreased and the propellants containing less than a certain AP content self‐quenched or did not ignite. The self‐quenched combustion began at both lower and higher pressures. The lower limit of AP content to burn the propellant with coarse AP was lower than that with fine AP. The lower limit of AP content to burn was decreased by the addition of Fe₂O₃. The thermal decomposition behavior of propellants prepared with 20–80 % AP was investigated. The decrease in the peak temperature of the exothermic decomposition suggested an increased burning rate. However, a quantitative relationship between the thermochemical behavior and the burning characteristics, such as the burning rate and the lower limit of AP content to burn, could not be determined.     

Utilization of New Non‐toxic Substances as Stabilizers for Nitrocellulose‐Based Propellants

Propellants consisting of nitrocellulose (NC) and/or other nitrate esters are inherently chemically unstable and undergo decomposition even under standard storage conditions. Decomposition of such compounds can be inhibited or nearly stopped when stabilizers are used. However, conventional stabilizers form nitrosamines that have toxic and carcinogenic effects. As a result, these conventional stabilizers should be replaced as soon as possible. A series of NC‐based propellants doped with different novel manufactured stabilizers were investigated using microcalorimetry, conventional stability tests, and sensitivity tests. The results were compared with propellants containing the conventional stabilizer Akardite II. The chemical structure of these new stabilizers and their decomposition products do not enable the formation of toxic N‐nitrosamines.     

Experimental and Computational Studies on the Thermal Degradation of Nitroazidobenzenes

In this combined experimental and theoretical study the thermal degradation of 2‐nitroazidobenzene ( I ), 2,4‐dinitroazidobenzene ( II ) and 2,4,6‐trinitroazidobenzene ( III ) to yield benzofuroxan ( IV ), 4‐nitrobenzofuroxan ( V ), and 4,6‐dinitrobenzofuroxan ( VI ) were investigated by thermoanalytical (TG, DSC) and computational methods. In contrast, furoxan formation was not observed for 4‐nitroazidobenzene ( VII ) under heating due to the para position of the nitro group in the benzene ring. All compounds were characterized by elemental analysis, vibrational (IR) spectroscopy and mass spectrometry. The crystal structure of compound III was determined by single‐crystal X‐ray diffraction. DFT‐based structure optimizations and frequency analyses were performed at the B3LYP/cc‐pVDZ level of theory. The structural parameters of the fully optimized compound III showed very good agreement with the single‐crystal X‐ray data. The enthalpies of formation for compounds I , II , III , IV , V , and VI were calculated using the complete basis set (CBS‐4M) method of Petersson and co‐workers in order to obtain accurate energies. The enthalpies of degradation for compounds I , II , and III were obtained from calculated enthalpies of formation according to the Hess Law and were compared with the experimental values, which were available from DSC analysis and were found to be in very good agreement.     

First Synthesis of Benzotrifuroxan at Low Temperature: Unexpected Behavior of 5,7‐Dichloro‐4,6‐dinitrobenzo‐furoxan with Sodium Azide

Attempts to prepare 5‐chloro‐6‐nitrobenzodifuroxan from the reaction of 5,7‐dichloro‐4,6‐dinitrobenzofuroxan with sodium azide have failed and, surprisingly, the formation of the powerful hydrogen‐free explosive – benzotrifuroxan (BTF) through spontaneous cyclization at 0 °C was observed (yield: 75 %). Importantly, BTF was synthesized avoiding the isolation and the heating of the hazardous intermediate trinitro‐triazidobenzene. The structure of BTF was confirmed by IR spectroscopy, elemental analysis, and melting point measurement.     

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.     

An Overview on the Synthetic Routes and Properties of Ammonium Dinitramide (ADN) and other Dinitramide Salts

In recent years, there has been a considerable interest in the development of novel type of high performance propellants for use in solid rocket motors. Ammonium salt of dinitramidic acid NH₄N(NO₂)₂ (ADN) has attracted wide interest as a potentially useful energetic oxidizer for rocket propellants because of its clean and environment‐friendly exhaust products during burning. ADN contains one N (NO₂)₂ group and its synthesis requires new type of N‐nitration. The present paper reviews the general synthetic methods used for the synthesis of inorganic, organic and metal dinitramide salts and their properties, with a special emphasis on ammonium dinitramide. The salient features with reference to the extent of conversion and ease of separation of the products of the various synthetic methodologies are also addressed.     

Effects of Nano-Aluminium on The Combustion of A PolyNIMMO-Based Propellant

Propellants containing micro-aluminium particles have been shown to produce faster burn rates than conventional gun propellants.However,they are also more abrasive than conventional propellants.Nano-ma...     

Energetic Opportunities of Solid Composite Propellants Containing Some Hypothetic Furazano-[3,4-d]-pyridazine-based Derivatives

Six furazano-[3,4-d]-pyridazine-based derivatives as main compounds in solid composite propellants have been investigated. It was shown that the use of some furazano-[3,4-d]-pyridazine-based derivatives as main compounds in solid composite propellants can considerably increase ballistic parameters compared with HMX if the compounds under consideration contain difluoramine groups. And the use of the compounds under consideration may be successful only in the presence of an active binder and 10%-30% of AP or ADN as additional oxidizers.     

Effect of Porosity on the Burn Rate of a Gas‐Generating Composition

In the course of the development of an oxidizer‐based extruded composite propellant for use as gas generant, a simple model to describe and evaluate the actual porosity using simple methods was developed. It is briefly described and used to assess the influence of porosity on the burn rate of propellants produced. For the formulation studied the presence of microporosities does not seem to significantly influence the burn rate. On the other hand, volume fraction of porosities in extruded composition grains can exert a large influence and can increase considerably under thermal treatment with a resulting augmentation in burn rate.     

Burning Characteristics of Ammonium Nitrate‐based Composite Propellants Supplemented with MnO2

Ammonium nitrate (AN)‐based composite propellants have several major problems, namely, a low burning rate, poor ignitability, low energy, and high hygroscopicity. The addition of a burning catalyst proved to be effective in improving the burning characteristics of AN‐based propellants. In this study, the burning characteristics of AN‐based propellants supplemented with MnO₂ as a burning catalyst were investigated. The addition of MnO₂ is known to improve the ignitability at low pressure. The most effective amount of MnO₂ added (ξ) for increasing the burning rate is found to be 4 %. The increasing ratio with ξ is virtually independent of the burning pressure and the AN content. However, the pressure exponent unfortunately increased by addition of MnO₂. The apparent activation energy of the thermal decomposition for AN and the propellant is decreased by addition of MnO₂. From thermal decomposition kinetics it was found that MnO₂ could accelerate the thermal decomposition reaction of AN in the condensed phase, and therefore, the burning characteristics of the AN‐based propellant are improved.     

Research on the Combustion Properties of Propellants with Low Content of Nano Metal Powders

A comparison of various experimental results for combustionrelated properties evaluation, including burning rates, deflagration heat, flame structures and thermal decomposition properties, of AP/RDX/Al/HTPB composite propellants containing nano metal powders is presented. The thermal behavior of n‐Al (nano grain size aluminum) and g‐Al (general grain size aluminum i.e., 10 μm) heated in air was also investigated by thermogravimetry. The burning rates results indicate that the usage of bimodal aluminum distribution with the ratio around 4 : 1 of n‐Al to g‐Al or the addition of 2% nano nickel powders (n‐Ni) will improve the burning behavior of the propellant, while the usage of grading aluminum powders with the ratio 1 : 1 of n‐Al to g‐Al will impair the combustion of the propellant. Results show that n‐Al and n‐Ni both have a lower heating capacity, lower ignition threshold and shorter combustion time than g‐Al. In addition n‐Al is inclined to burn in single particle form. And the thermal analysis results show that n‐Ni can catalyze the thermal decomposition of AP in the propellant. The results also confirm the high reactivity of n‐Al, which will lead to a lower reaction temperature and rather higher degree of reaction ratio as compared with g‐Al in air. All these factors will influence the combustion of propellants.     

Preparation and Characteristics of Foamed NC‐Based Propellants

Foaming properties of the three NC‐based (nitrocellulose‐based) propellants, namely, single‐base propellant, NG (nitroglycerine) propellant and TEGDN (triethylene glycol dinitrate) propellant were investigated in the batch foaming process by using supercritical CO₂ as the physical foaming agent. Burning characteristics of the foamed NC‐based propellants were also investigated in this work. For this study, the CO₂ desorption of the three NC‐based propellants were plotted by the gravimetric method. The morphology and burning characteristics of these foamed NC‐based propellants were characterized by scanning electron microscope (SEM) and closed vessel experiment. The test data revealed that the energetic plasticizer has a considerable effect on the pore formation in the NC matrix although it has little effect on the CO₂ solubility in the NC‐based propellants. Moreover, the SEM images showed the foaming temperature also plays an important role in the pore parameters of foamed propellants. Furthermore, the data of closed vessel experiment indicated that the burning characteristics of foamed NC‐based propellants largely depend on the pore parameters, and the porous structure of foamed propellants would considerably increase the mass conversion rate.     

A Study on the Effect of Additives on Temperature Sensitivityin Composite Propellants

The hydroxy‐terminated polybutadiene (HTPB) based composite propellants without any metal additive and with varying concentration of metal additives such as iron oxide, copperchromite, strontium carbonate and lithium fluoride have been cast and cured. These propellants have been characterized for density and calorimetric value (cal‐val). Further, their temperature sensitivity has also been determined from the burning rates calculated from the P‐t profiles obtained on static evaluation of Ballistic Evaluation Motor (BEM) after conditioning at different temperatures. The data indicate that iron oxide is best to enhance burning rates and at the same time, to reduce temperature sensitivity.     

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.     

Burning Characteristics of Consolidated Gun Propellants

To improve the combustion behaviors of conventional consolidated propellants, consolidated propellants were prepared using porous propellant grains as fast‐burning filler. The porous propellant grains were prepared by supercritical fluid foaming process and exhibited the high burning rate. The multi‐perforated structure of the consolidated propellants was designed and adopted to obtain high burning progressivity. To investigate the burning characteristics of the consolidated propellants, closed vessel and quenched combustion experiments were carried out. The results show that deconsolidation of the consolidated propellants does not occur, and that the consolidated propellants exhibit high burning rates and high burning progressivities. Besides, the results show that the consolidated propellants burn steadily even at low (−40 °C) and high temperatures (50 °C).