Mechanical and burning properties of highly loaded composite propellants

An improvement in the performance of solid rocket motors was achieved by increasing the oxidizer content of HTPB-based solid propellants. To minimize the adverse changes in the mechanical and rheological properties due to the increased amount of hard solid particles in the soft polymeric binder matrix, the optimum combination of the particle sizes and volume fractions of the bimodal ammonium perchlorate and the aluminum powder in the solid load was obtained from the results of testing a series of propellant samples prepared by using ammonium perchlorate in four different average particle sizes, 9.22, 31.4, 171, and 323 μm. The maximum packing density of solids in the binder matrix was determined by changing the sizes and the volume fractions of fine and coarse ammonium perchlorate at constant solid loading. The average size (10.4 μm) and concentration of aluminum powder used as metallic fuel were maintained constant for ballistic requirements. Optimum sizes and fine-to-coarse ratio of ammonium perchlorate particles were determined to be at mean diameters of 31.4 and 323 μm and fine-to-coarse ratio of 35/65. Solid content of the propellant was then increased from 75 to 85.6% by volume by using the predetermined optimum sizes and fine to coarse ratio of ammonium perchlorate. Mechanical properties of the propellant samples were measured by using an Instron tester with a crosshead speed of 50 mm/min at 25°C. The effect of oxidizer content and fine-to-coarse ratio of oxidizer on the burning rate of the propellant was also investigated by using a strand burner at various pressures. From experiments in which the size and the fine-to-coarse ratio of ammonium perchlorate were changed at constant solid loading, a minimum value of initial modulus was obtained for each fine-to-coarse ratio, indicating that the solids packing fraction is maximum at this ratio. The tensile strength and the burning rate increase, while the elongation at maximum stress decreases with increasing fine-to-coarse ratio of ammonium perchlorate. Experiments in which the total solid loading was increased at constant fine-to-coarse ratio of ammonium perchlorate show that the modulus, the tensile strength and the burning rate increase, while the elongation at maximum stress decreases with increasing solid loading. Propellants having solid loading of up to 82% exhibit acceptable mechanical properties and improved burning properties suitable for rocket applications. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1457–1464, 1998     

Effect of Voids inside AP Particles on Burning Rate of AP/HTPB Composite Propellant

Bubble contamination in an ammonium perchlorate (AP)‐based composite propellant has a positive effect on the burning rate. However, the quantitative effect of the bubble contamination on the burning rate has never been revealed. In order to clarify the relationship between the increase in the burning rate and the void fraction of the propellant, propellants were prepared with fine porous AP particles (PoAP) or fine hollow AP particles (HoAPs), and their burning rate characteristics were investigated. The voids inside AP particles have the effect of increasing the burning rate. The increase in the burning rate is enhanced linearly as the void fraction increases. The effect of the void fraction on the burning rate for a propellant containing PoAP is not identical with that for a propellant containing HoAP. It was found that the effect of the void fraction on the burning rate could be estimated by the void fraction when the bubble contamination is uniform in size and shape.     

Burning Behavior of Composite Solid Propellant containing porous ammonium perchlorate

A pilot scale fluidized bed process was developed for preparing porous ammonium perchlorate (PAP) in various particle sizes. The oxidizer, ammonium perchlorate (AP), of composite solid propellant was partially replaced by PAP which was obtained by the fluidization process. The burning rate of propellants containing PAP was found to increase as compared with that of propellants without PAP. In the present study, the effects of percentage content and particle size of PAP incorporated in propellant compositions, on the burning rate were investigated. The results showed that the burning rate increases with increasing of PAP content and with decreasing of PAP particle size for trimodal oxidizer propellants.     

Ammonium Perchlorate,Friend or Foe? Part 1: The Influence of this Oxidizer on the Aging Behavior of Propellant Compositions

Propellants containing nitroglycerine and ammonium perchlorate have been reported to have comparatively shorter shelf lives than analogous energetic materials without this oxidizer. However, investigation into the aging behavior of three compositions containing polyethylene glycol and nitroglycerine revealed that the propellant which included ammonium perchlorate degraded at a slower rate compared with the other materials. It was suggested that ammonium perchlorate might act as an oxygen inhibitor reducing the oxidation rate of the polyethylene glycol binder so decreasing the rate of the propellant decomposition. In addition, at temperatures of 80 °C or lower, ammonium perchlorate initially appears to hinder acid hydrolysis of nitroglycerine which also slows down the degradation of polyethylene glycol based propellant.     

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.     

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.     

Effects of Additives on the Ignition of AP-Based Propellants at subatmospheric pressures

The ammonium perchlorate (AP)-oxidized composite propellants, each of which contains separately copper chromite (CC) as a burning rate adjuster and carbon black (CB) as an opacifier, have been ignited at subatmospheric pressures of argon gas by means of a carbon dioxide laser, and the effects of the additives on the ignition behavior have been studied. It has been found that copper chromite shortens the ignition time especially below 100 torr and that at the same time it enhances the ignitability, i.e., self-sustaining ignition. Carbon black, being an opacifier decreasing reflectivity and increasing radiative absorption at propellant surface, can not be recognized to be an active catalyst in ignition at subatmospheric pressures. The data of differential thermal analysis (DTA) for above specimens have indicated that the maximum exothermic peak temperature is shifted toward a lower one with the increase in CC concentration, the exothermic peak structure becoming sharper. However, CB addition to the basic propellant makes exothermic peaks less distinct. The results of DTA support those obtained from the ignition experiments above.     

Role of Boron in Burning Rate Augmentation of AP composite propellants

Effect of the addition of boron particles on the burning rate of solid propellants was examined. The propellants tested in this study consisted of ammonium perchlorate (AP) as an oxidizer and carboxyl terminated polybutadiene as a fuel binder. The propellant burning rate is increased significantly by the addition of a small amount of boron particles. The burning rate augmentation is dependent largely on the size and concentration of the boron particles mixed. Thermochemical experiments revealed that the boron particles react with the decomposed gases of AP on and just above the propellant burning surface. The heat flux transferred back from the gas phase to the burning surface of the propellant increases with increasing the total surface of the boron particles mixed within the unit mass of propellant. The burning rate augmentation is correlated to the heat of reaction generated by the oxidation reaction of boron particles.     

RDX-CMDB推进剂燃速温度敏感系数的实验研究

为了揭示RDX-CMDB推进剂中各常见组分对其燃速温度敏感系数的影响规律,制备了一系列含RDX、铝粉及燃烧催化剂的CMDB推进剂样品。采用氮气靶线法测得其在2~14MPa下的燃速温度敏感系数(σp)。讨论了RDX含量、铝粉、燃烧催化剂对RDX-CMDB推进剂燃速温度敏感系数的影响。结果表明,提高工作压强、增加RDX含量、添加燃烧催化剂均有助于降低RDX-CMDB推进剂在一定初始条件下的燃速温度敏感系数。配方中引入铝粉后可降低中低压下RDX-CMDB推进剂的燃速温度敏感系数,且燃速温度敏感系数几乎不随压强变化而变化。选用含邻苯二甲酸铅和没食子酸铋锆作燃烧催化剂,均可在2~10MPa下降低RDX-CMDB推进剂的燃速压强指数,同时降低燃速温度敏感系数。     

On-demand microwave growth of porosity within a granular composite energetic material: Void formation via a dielectric loss phase change binder additive for propellant burning rate control

This study demonstrates, for the first time ever, the ability to grow, in an on-command fashion, porosity within a granular composite energetic material to effect a change in energy output rate. Specifically, the study investigates the change in burning rates of ammonium perchlorate composite propellants as a result of porosity created in situ via microwave field-driven volatilization of the low boiling point binder additive, ethylene glycol. Theoretical mass densities were measured before and after microwave irradiation finding that the maximum observed %TMD change for tested propellants is 6 %. Propellants were burned at 1.72 MPa to 6.89 MPa pressures, finding that for all propellants, microwave irradiation produced a change in ballistic characteristics. Most propellant formulations demonstrate acceptable burning rate parameters for use within rocket motors; some exhibited a large change in their pressure exponent as well as slope breaks attributed to the onset of convective burning, while microwave irradiation produced no change in burning rate or density in reference propellants without the additive. Microwave heating simulation results are presented to gain insight into the thermal environment of the propellant during microwave irradiation. These results provide valuable insight into propellant formulations that can have their burning rates (and thus the thrust profile for motor grains) altered after casting via microwave irradiation.     

Agglomeration Characteristics of Aluminum Particles in AP/AN Composite Propellants

Most solid rockets are powered by ammonium perchlorate (AP) composite propellant including aluminum particles. As aluminized composite propellant burns, aluminum particles agglomerate as large as above 100 μm diameter on the burning surface, which in turn affects propellant combustion characteristics. The development of composite propellants has a long history. Many studies of aluminum particle combustion have been conducted. Optical observations indicate that aluminum particles form agglomerates on the burning surface of aluminized composite propellant. They ignite on leaving the burning surface. Because the temperature gradient in the reaction zone near a burning surface influences the burning rate of a composite propellant, details of aluminum particle agglomeration, agglomerate ignition, and their effects on the temperature gradient must be investigated. In our previous studies, we measured the aluminum particle agglomerate diameter by optical observation and collecting particles. We observed particles on the burning surface, the reaction zone, and the luminous flame zone of an ammonium perchlorate (AP)/ammonium nitrate (AN) composite propellant. We confirmed that agglomeration occurred in the reaction zone and that the agglomerate diameter decreased with increasing the burning rate. In this study, observing aluminum particles in the reaction zone near the burning surface, we investigated the relation between the agglomerates and the burning rate. A decreased burning rate and increased added amount of aluminum particles caused a larger agglomerate diameter. Defining the extent of the distributed aluminum particles before they agglomerate as an agglomerate range, we found that the agglomerate range was constant irrespective of the added amount of aluminum particles. Furthermore, the agglomerate diameter was ascertained from the density of the added amount of aluminum particles in the agglomerate range. We concluded from the heat balance around the burning surface that the product of the agglomerate range and the burning rate was nearly constant irrespective of the added amount of aluminum particles. Moreover, the reduced burning rate increased the agglomerate range.     

Temperature sensitivity of Burning Rate of Ammonium Perchlorate Propellants

The temperature sensitivity of burning rate of ammonium perchlorate (AP) composite propellants was studied as a function of AP particle size and a burning rate catalyst. A simplified temperature sensitivity model was presented in order to discriminate the effect of the gas phase and solid phase reactions on the initial propellant temperature (T₀). The temperature sensitivity was decreased by the addition of small sized AP particles and/or 2,2-bis(ethylferrocenyl)propane (BEFP). This is caused by the insensitive burning surface temperature to T₀. Thus, the gas phase reaction rate becomes little dependent on T₀, and the temperature sensitivity decreases.     

Reducing Agglomeration of Ammonium Perchlorate Using Activated Charcoal

Ammonium perchlorate is the most widely employed oxidizer for composite solid propellants. When exposed to atmosphere, it absorbs moisture and agglomerates. It is usually vacuum dried in order to avoid this agglomeration. When ammonium perchlorate that has been exposed to atmosphere for a certain period of time, is used in making a composite solid propellant, the burning rate is different because of the change in particle size distribution due to its agglomeration. This change in burning rate will change the thrust‐time profile from that of what it is designed for. As one goes to a finer ammonium perchlorate particle size this problem becomes more evident. Experimental studies aimed at reducing the agglomeration of ammonium perchlorate by coating it with activated charcoal. Ammonium perchlorate coated with 1 % activated charcoal showed almost no agglomeration, even when the particle size of ammonium perchlorate is approx. 1 μm. The burning rates also remained unchanged when ammonium perchlorate coated with 1 % activated charcoal was employed in propellant composition, after it has been exposed to the atmosphere for a period of 1 h.     

B12H12［N(C2H5)4］2对NEPE推进剂燃烧性能的影响

研究了硼氢化合物 B1 2 H1 2 [N(C2 H5 ) 4] 2 对 NEPE推进剂燃烧性能的影响 ,采用 DSC分析了 B1 2 H1 2 [N(C2 H5 ) 4] 2 与 NEPE推进剂主要组分硝酸酯的相容性以及对推进剂固化反应的催化作用和对高氯酸铵、硝胺常压热分解的催化作用 ,并利用恒压静态燃速仪测试了推进剂在 4～ 1 1 MPa的燃烧速度和燃速压力指数     

含相稳定硝酸铵CMDB推进剂的机械感度和燃烧性能

通过测试撞击感度、摩擦感度和燃速,研究了含相稳定硝酸铵(PSAN)的改性双基(CMDB)推进剂的燃烧性能和机械感度。结果表明,PSAN可改善CMDB推进剂的机械感度;用PSAN作氧化剂,其推进剂的燃速低于RDX作氧化剂的燃速,压强指数高于后者的压强指数;1～5MPa压力范围内随PSAN在配方中含量的增加,推进剂的燃速降低,压强指数升高。     

Storage stability of solid rocket fuel. 1. Effect of temperature

Ageing behaviour of polystyrene (PS)/ammonium perchlorate (AP) propellent leading to ballistic changes has been studied. It follows a zero-order kinetic law. Ageing behaviour leading to change in burning rate ($\text{r}\text{?}$) in the temperature range of 60–200 ° C was found to remain the same. The dependence of the change of the average thermal decomposition (TD) rate at 230 and 260°C on the change in burning rate for the propellant aged at 100 ° C in air suggests that the slow TD of the propellant is the cause of ageing. The safe-life (for a pre-assigned burning-rate change limit) at 25 ° C in air has been calculated as a function of the rate of change.     

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.     

Composite Propellant Based on a New Nitrate Ester

Composite propellants based on the solid nitrate ester 2,3‐hydroxymethyl‐2,3‐dinitro‐1,4‐butanediol tetranitrate (SMX) were theoretically and experimentally examined and compared to formulations based on ammonium perchlorate (AP). Thermochemical equilibrium calculations show that aluminized SMX‐based formulations can achieve theoretical sea level specific impulse values upwards of 260 s. Both ignition sensitivity (tested via drop weight impact, electrostatic discharge, and BAM friction) and physical properties (hardness and thermal properties) are comparable to those of the AP‐based formulations. However, the SMX‐based formulation could be detonated using a high explosive donor charge in contact with the propellant. Differential scanning calorimetry of the SMX‐based propellant indicated an exotherm onset of 140 °C, which corresponds to the known decomposition temperature of SMX. The propellant has a high burning rate of 1.57 cm s⁻¹ at 6.89 MPa, with a pressure exponent of 0.85. This high pressure sensitivity might be addressed using various energetic and/or stabilizing additives. With good performance and high density, SMX‐based composite propellants may offer a promising perchlorate‐free alternative to existing AP‐based formulations.     

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.     

Plateau Burning Characteristics of AP Based Azide Composite Propellants

The site and mechanism by which iron oxide catalyst acted to enhance burning rate and produced plateau burning behavior at high pressure was studied. The condensed phase chemistry study was conducted by isothermal thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), and rapid-scan FTIR spectroscopic technique. Uncatalyzed ammonium perchlorate (AP) based azide composite propellant showed unstable combustion at relatively lower pressure region. The heat balance at the buring surface would be unstable at these pressures. However, iron oxide altered the burning property of the propellant and enhanced the burning rate with the plateau-mesa burning characteristics. Such pressure insensitiveness of the burning rate indicated that the condensed phase chemistry played important role in the catalytic mechanism of action. According to the microrocket motor tests, physical effect, melted fuel binder covered the AP particles and prevented the further decomposition of AP, had not affected the plateau burning. Fe₂O₃ was more effective on the burning rate augmentation than Fe₃O₄. However, the pressure exponent of the burning rate point of view Fe₃O₄ was favored catalyst to the propellant used here.