Influence of Particle Size on the Combustion of CL‐20/HTPB Propellants

The effect of nitramine particle size on the combustion behavior of inert binder based propellants has been extensively studied for RDX and HMX, but not CL‐20. Although materials such as RDX and HMX are useful for particular combustion applications, CL‐20 has a greater potential to improve the oxygen balance and energy density of a propellant. The current work investigates the effect of CL‐20 particle size on the combustion of CL‐20/HTPB propellants down to submicrometer sizes. An influence of particle size on the burning rate and combustion mechanism is reported. The 30 micrometer formulation burning rate data showed evidence of convective burning specifically at higher pressures, but the pressure dependence was comparable to neat CL‐20 at pressures below 8 MPa. A change in the combustion mechanism of the submicrometer formulation as a function of pressure was determined to be a result of the interaction of the propellant flame and the combustion residue. Data suggested that at low pressures diffusion in terms of active cooling was dominant for the submicrometer formulation. Higher pressure data for both the submicrometer and 3 micrometer formulations suggest the degree of active cooling is decreased as the burning rate pressure exponent is near 0.5 for both propellants. The indirect evidence for the presence of a melt layer for CL‐20 propellants is discussed.     

Ballistic Modification of Nitramine Propellants with Special Reference to NG‐PE‐PCP‐Based High Energy Propellants

The burning rate pressure relationship is one of the important criteria in the selection of the propellant for particular applications. The pressure exponent (η) plays a significant role in the internal ballistics of rocket motors. 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/AP/Al‐ and NG/PE‐PCP/HMX/AP/Al‐based solid rocket propellants processed by a conventional slurry cast route were carried out. The objective of present study was to understand the effectiveness of various ballistic modifiers viz. iron oxide, copper chromite, lead/copper oxides, and lead salts in combination with carbon black as a catalyst on the burning rate and pressure exponent of these high‐energy propellants. A 7–9 % increase in the burning rates and almost no effect in pressure exponent values of propellant compositions without nitramine were observed. However, in case of nitramine‐based propellants as compared to propellant compositions without nitramines, slight increases of the burning rates were observed. By incorporation of ballistic modifiers, the pressure exponents can be lowered. The changes in the calorimetric values of the formulations by addition of the catalysts were also studied.     

Investigation of the Burning Behavior of Cryogenic Solid Propellants

Cryogenic Solid Propellant (CSP)‐technology is a new approach to develop more powerful rocket motors. CSPs include the advantages of classical solid propellants to save weight as well as those of a high energy content and safety of modern liquid propellants. The charges consist of liquid and/or gaseous fuels and oxidizers, both frozen. Two main versions of CSP‐technology can be realised: 1. Mono‐CSPs show the burning behavior of solid propellants. Experiments with mono‐CSPs have been carried out under inert pressure conditions in a window bomb. Mono‐CSPs have a stable burning behavior with a constant regression rate which follows the Vieille's law under varying pressure conditions. 2. The advantage of high safety is obtained by assembling oxidizer and fuel in sandwich configurations. The grain geometry governs the burning behavior. Such systems can be externally controlled, e.g. by the heat from a gas generator or they can work self‐sustained. A Rod‐in‐Matrix burner shows self‐sustained combustion in an inert pressure atmosphere with overall burning rates in a similar range as solid rocket propellants which obey also a Vieille‐like pressure law. Disc stack burners have also been investigated, the combustion of which is strongly dependent on the disc thickness. For a short time Mach's nodes have been observed in the exhaust plume of a disc stack burner. Currently, the temperature ranges are limited to the boiling temperature of liquid nitrogen. Therefore, liquid oxidizers like H₂O₂ have been used. However, for the first time a propellant strand of polymer rods embedded in solid oxygen was prepared and burnt. The experiments with CSPs end in the combustion of a small rocket motor showing no serious technical obstacles. Simplified models based on the heat flow equation can simulate the burning characteristics of the frozen energetic materials including phase transitions.     

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.     

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.     

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.     

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).     

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.     

Performance Parameters of Explosives: Equilibrium and Non‐Equilibrium Reactions

For the calculation of the performance parameters of combustion processes, equilibrium thermodynamic processes are taken into account. On the other hand, non‐equilibrium reactions occur, mostly connected with low pressure burning. In this paper, several explosives, explosive mixtures, solid and liquid propellants have been calculated. It is shown how energy output and gas formation depend on the oxygen balance and the enthalpy of formation. It was found that the reason for the higher specific energy of liquid propellants is due to the increased formation of gases consisting of H₂, N₂ and H₂O, compared with conventional solid propellants based on nitrocellulose and nitroglycerin, which produce more CO and CO₂. Non‐equilibrium combustion of solid propellants was found at very low loading densities or pressures lower than 1 to 2 MPa. In this case, the reaction products measured by mass spectrometry, such as NO, N₂O and HCN, are metastable and highly toxic, producing a much lower heat of explosion compared with equilibrium burning measured and calculated.     

Iron Nanoparticle Additives as Burning Rate Enhancers in AP/HTPB Composite Propellants

Burning rate measurements were carried out for ammonium perchlorate/hydroxyl‐terminated polybutadiene (AP/HTPB) composite propellants with iron (Fe) nanoparticles as additives. Experiments were performed in a strand burner at pressures from 0.2 to 10 MPa for propellants containing approximately 80 % AP and Fe nanoparticles (60–80 nm) at concentration from 0 to 3 % by weight. It was found that the addition of 1 % Fe nanoparticles increased burning rate by factors of 1.2–1.6. Because Fe nanoparticles are oxidized on the surface and have high surface‐to‐volume ratio, they provide a large surface area of Fe₂O₃ for AP thermal decomposition catalysis at the burning propellant surface, while also providing added energy release due to the oxidation of nanoparticle sub‐shell Fe. The increase in burning rate due to Fe nanoparticle content is similar to the increase in burning rate caused by the addition of iron oxide (Fe₂O₃) particles observed in prior literature.     

The Effects of Porous Structure on the Burning Characteristics of Foamed NC‐Based Gun Propellants

The effects of porous structure on the burning characteristics of foamed NC‐based (nitrocellulose‐based) gun propellants were investigated by closed vessel and quenched combustion experiments. The foamed NC‐based TEGDN (triethylene glycol dinitrate) gun propellants with different porous structures were prepared by adjusting the process parameters in the foaming process. SEM (scanning electron microscopy) was used to observe the morphologies of foamed TEGDN propellants, and the densities of the foamed propellants were also measured to evaluate the porosities of foamed propellants. The experimental results showed that the burning characteristics of the novel foamed propellants are totally different from combustion characteristics of parallel‐layer. Further investigations revealed that the burning characteristics of the foamed NC‐based propellants largely depend on the porous structure, larger pores and higher porosity would lead to higher burning rate of the foamed TEGDN propellants.     

Combustion Characteristics of a Novel Grain‐Binding High Burning Rate Propellant

The novel grain‐binding high burning rate propellant (NGHP) is prepared via a solventless extrusion process of binder and spherical propellant grains. Compared with the traditional grain‐binding porous propellants, NGHP is compact and has no interior micropores. During the combustion of NGHP, there appear honeycomb‐like burning layers, which increase the burning surface and the burning rate of the propellant. The combustion of NGHP is a limited convective combustion process and apt to achieve stable state. The larger the difference between the burning rate of the binder and that of the spherical granular propellants exists, the higher burning rate NGHP has. The smaller the mass ratio of the binder to the spherical granular propellants is, the higher the burning rate of NGHP is. It shows that the addition of 3 wt.‐% composite catalyst (the mixture of lead/copper complex and copper/chrome oxides at a mass ratio of 1 : 1) into NGHP can enhance the burning rate from 48.78 mm⋅s⁻¹ in the absence of catalyst to 56.66 mm⋅s⁻¹ at P=9.81 MPa and decrease the pressure exponent from 0.686 to 0.576 in the pressure range from 9.81 to 19.62 MPa.     

Burning Rate Augmentation of BAMO Based Propellants

Thermal decomposition and the burning properties of BAMO based propellants with HMX or AN/HMX have been investigated. The heat generated by the azide binder decomposition initiated and accelerated the thermal decomposition of HMX and AN. Ammonium perchlorate (AP) and lead stearate with carbon black significantly altered the mechanisms of the thermal decomposition and the burning properties of the HMX based propellants. AP showed an increase in burning rate with a slight decrease in burning rate pressure exponent. The lead catalyst yielded high value of the burning rate with the lowest pressure exponent. The ammonium dichromate also influenced the mechanisms of the thermal decomposition and the burning properties of the AN/HMX samples. The combination of ammonium dichromate and copper chromite was the most effective on the burning rate augmentation of AN/HMX based propellants. AN sublimed and evaporated from the condensed phase and mainly reacted exothermically in the gas phase HMX and AN/HMX based propellants showed smokeless burning characteristics in the small rocket motor combustion tests.     

Interrupted‐Burning Tests of Plasma‐Ignited JA2 and M30 Grains in a Closed Chamber

Enhanced burning of plasma‐ignited propellants has been deduced in recent years from closed bomb pressure traces. The question remains, however, whether the enhanced burning is inherent or possibly the result of propellant grain fracture. To find out, interrupted and non‐interrupted burning tests were conducted with cylindrical perforated grains of JA2 and M30 in a closed bomb with a loading density of approximately 0.2 g/cm³. Both, conventional black powder and plasma igniters were used, and a few tests were carried out with the propellants cooled to −20 °C. The plasma igniter was an ablating capillary, and the electrical energy density was about 0.7 kJ/g of propellant. The diameters of the collected grains yielded the actual burn distance at the time of the interrupted burning. The experimental pressure traces and the conventional burn rate coefficients of the propellants were used to calculate the theoretical depth burned assuming no plasma‐induced burn rate modifications. From overlapping pressure traces at several interrupted pressures, and from comparison to the calculated versus measured burn distances, it was found that there is burn rate enhancement during the plasma pulse–but not much once the pulse has ended. In contrast to the JA2 burn rates, both ambient and cold M30 burn rates, deduced from the non‐interrupted tests using the BRLCB code, were enhanced even after the plasma turn‐off, thus contradicting the interrupted‐tests results. However, vivacity analysis of the non‐interrupted tests indicated that the M30 grains exhibited increased surface area (possible fragmentation) because of the plasma interaction–an effect that would cause erroneous results from the BRLCB. Indeed, simulation of the non‐interrupted M30 tests using the XNOVAKTC code, and assuming partial fragmentation of the propellant charge, yielded vivacities that mimicked the experimental ones.     

Ammonium perchlorate-based composite solid propellant formulations with plateau burning rate trends

This paper presents burning rates as a function of pressure of several propellant formulations based on ammonium perchlorate (AP) and hydroxyl-terminated polybutadiene cured by isophorone diisocyanate, many of which exhibit significantly low (nearly zero or negative) values of the pressure exponent of the burning rate in distinct pressure ranges, termed as plateau burning rate trends. The propellants contain a bimodal distribution of AP particles with the size of the coarse and fine particles within narrow ranges whose mean values are widely separated. Two mean sizes of fine particles were considered for the propellant formulations in the present work, namely, 5 and 20 μm. These choices are based on the mid-pressure extinction behavior exhibited by the matrix of fine AP and binder contained in the propellants but when tested alone over a wide range of fine AP size and pressure. The propellants that include the fine AP/binder matrixes exhibiting a mid-pressure extinction, in turn, exhibit the plateau burning rate trends within the corresponding pressure ranges. A plateau is also observed at elevated pressures in the burning rates of some formulations, which is related to the diminishing relative importance of the near-surface leading-edge region of the oxidizer/fuel diffusion flame in the gas-phase combustion zone. The choice of the coarse AP size influences the exact pressure range within the mid-pressure extinction domain of the matrix where the propellant exhibits the plateau burning rate trends. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 4, pp. 73–81, July–August, 2007.     

Burning Rates and Thermal Behavior of Bistetrazole Containing Gun Propellants

The influence of two selected bistetrazoles, 5,5′‐bis(1H‐tetrazolyl)‐amine (BTA) and 5,5′‐hydrazinebistetrazole (HBT), on the combustion behavior of a typical triple‐base propellant was investigated. Seven propellant formulations, one reference and six others incorporating 5 %, 15 %, and 25 % of either HBT or BTA compounds, respectively, were mixed and extruded into a cylindrical, no perforations, geometry. The resulting propellants showed high burning rates, up to 93 % higher than the reference formulation at 100 MPa. However, the increase in burning rates came at the cost of higher burning rate dependency on pressure, with a pressure exponent as high as 1.4 for certain formulations. HBT‐containing propellants showed notably lower flame temperature when compared to the reference formulation, with a flame temperature reduction of up to 461 K for the propellant containing 25 % HBT. The thermal behavior of the propellants was also investigated through DSC experiments. The addition of bistetrazoles provided lower decomposition temperatures than the pure nitrogen‐rich materials, indicating that the two compounds probably react readily with the −ONO₂ groups present in the nitrocellulose and the plasticizers used in the formulation. The onset temperature of all propellants remained within acceptable ranges despite the observed decrease caused by the addition of the bistetrazole compounds.     

Burning of hydroxylammonium nitrate

Burning of solid crystalline hydroxylammonium nitrate (HAN) and its water solutions is studied in a constant-pressure bomb within the pressure range from 0.1 to 36 MPa. Abnormally high pressure exponents are found to be typical of combustion of the crystalline substance, its ≈9-mole/liter water solution, and a solution containing ethanolamine nitrate as a fuel: for pressures below ≈10 MPa, the burning rate is proportional to the 1.5–2.6 power of pressure. Crystalline HAN retains this tendency up to ≈20 MPa, whereas the solutions burning in the turbulent regime show a sharp decrease in the pressure exponent if the pressure exceeds 10 MPa. In some instances, as was found in previous works, the burning rate even decreases with increasing pressure. Special features of turbulent burning are explained. A model is proposed to describe the steady-state burning of solid HAN. Kinetic parameters of the leading reaction are derived. Translated fromFizika Goreniya i Vzryva, Vol. 36, No. 1, pp. 149–160, January–February, 2000. This work was partly supported by the Russian Foundation for Fundamental Research (Grant Nos. 98-32164 and 98-32167).     

泡孔结构对泡沫发射药燃烧性能的影响

通过配方调节与工艺控制得到3种不同结构的泡沫发射药,讨论了泡孔结构形成的影响因素;采用密闭爆发器实验和恒压燃速测试实验研究了不同结构泡沫发射药的燃烧性能。结果表明,控制气体生成速率、添加RDX颗粒、调节NC含氮量和发泡时间能够有效控制泡沫发射药的泡孔结构;皮芯结构泡沫发射药具有渐增燃烧特性,发泡区的动态活度可达不发泡皮层的2.4倍以上;独立泡孔结构的泡沫发射药在100MPa下燃速可达未发泡样品的30倍;非独立孔隙结构的泡沫发射药不同方向上的燃速差异显著,密度为1.37g/cm~3的样品100MPa下轴向燃速最高可达3.860m/s。     

Aluminum Agglomeration on Burning Surface of NEPE Propellants at 3–5 MPa

Aluminum agglomeration and agglomerate sizes of NEPE propellants were studied by cinephotomicrography at pressures of 3 and 5 MPa. Accumulation, aggregation, and agglomeration of aluminum particles similar to that at pressures below 1 MPa were observed. Coalescence of two agglomerates on the burning surface is obtained for the first time. A decrease in the burning rate from 8 to 5 mm s⁻¹ leads to about 20 % increase in the agglomerate diameter. The pressure is found to have no direct influence on the agglomerate diameter when the burning rate is kept constant. The evolution of the agglomerate diameter according to the increase of the virgin aluminum size from 16 to 36 μm is convex in shape and reached its maximum at a particle diameter of 29 μm. Increasing the amount of RDX crystals added in the propellants causes a larger agglomerate diameter. The experimental mass average agglomerate diameters were compared with various agglomeration models. It is found that Hermsen and Salita empirical models have a higher accuracy for NEPE propellants rather than Becksted, Liu, or pocket models.     

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.