CL-20含量及其粒度级配对NEPE推进剂燃烧性能的影响

采用静态与水下声发射法测试了CL-20含量及其粒度级配对NEPE推进剂燃速与压强指数的影响;采用DSC与TG-IR联用研究了CL-20对NEPE推进剂热分解行为的影响。结果表明,随着CL-20质量分数由42%增至50%,推进剂燃速与压强指数上升,燃烧效率提高,表明CL-20氧化能力高于GAP/硝酸酯含能黏合剂体系;随着CL-20/HMX、CL-20/Al质量比增高,推进剂燃速上升,燃烧效率上升;CL-20对推进剂燃速和压强指数的贡献高于HMX;随着CL-20/AP质量比增高,CL-20/AP混合体系分解产物氧化能力降低,燃烧反应速率降低,燃速降低;CL-20粒度级配对NEPE推进剂燃烧行为影响显著,当CL-20的粒径(d50)在5~50μm时,随着细粒度CL-20含量增高,推进剂燃速与燃速压强指数下降;当体系中存在超细粒度CL-20(d50=500nm)时,推进剂燃速与燃速压强指数随着超细粒度CL-20含量的增加而有所增加,4种粒度CL-20对NEPE推进剂燃速的贡献顺序为:粗粒度>中粒度>超细粒度>细粒度。     

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.     

Studies on RDX Particle Size in LOVA Gun Propellant Formulations

This paper presents the results of systematic studies carried out on the role of fine RDX in determining the burning rate and ballistics of LOVA gun propellants. Propellant formulations containing fine RDX particles with a size of 4.5, 6, 13 and 32 µm as energetic ingredient, cellulose acetate as inert binder, triacetin as inert plasticizer, nitrocellulose of lower percentage nitrogen content as energetic binder and carbamite as stabilizer were made. The evaluation of the propellant batches has been carried out by static firing using closed vessel technique. It indicates the linear relation between the burning rate of the propellant and the fine RDX particle size used in this formulation. The results of the present studies revealed that fine RDX of 4.5 to 6 µm size may be the most suitable for LOVA gun propellant to meet the desired burning rate for satisfactory ballistics.     

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.     

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.     

Surface layer dynamics in the pyrolysis of ammonium perchlorate-hydrocarbon binder propellants

Mixtures of ammonium perchlorate particles and polybutadiene binder appear to exhibit preferential accumulation of one or the other component on the pyrolyzing surface over a range of rocket-operating pressures. At low pressures, the surface layer is enriched with the oxidizer, and at high pressures, it is enriched with the binder. The degree of accumulation of the oxidizer is found to be higher for smaller particle size. These experimental data can be explained by the difference in activation energies for pyrolysis of the oxidizer and the binder. The particle size effect is explained by consideration of nearly identical surface temperatures for the oxidizer and binder in mixtures with fine particles, but different temperatures for those with coarse particles. The results obtained are important to the explanation of the mechanism of plateau burning rate exhibited by certain composite propellants. Translated fromFizika Goreniya i Vzryva, Vol. 36, No. 5, pp. 57–62, September–October, 2000.     

Flammability limits and ballistic properties of fuel-rich propellants

The flammability limits and ballistic properties of composite fuel-rich propellants were studied experimentally, using PBAN/AP propellant formulations. Higher pressure and AP contents as well as smaller AP particle size were found to promote sustained combustion and to increase burning rate. The addition of potassium perchlorate (KP) in place of AP increased the burning rate pressure exponent from about 0.3 to over 0.7 at optimum conditions. Ferric oxide and copper chromite catalysts caused an increase of the burning rate by a factor of 2, while the addition of aluminum powder at the expense of the fuel binder was found to have a remarkable effect on the burning rate with a maximum increase of as high as 5-fold.     

Effect of Binders on the Burning Rate of AP Composite Propellants

The burning rate characteristics of ammonium perchlorate (AP) based composite propellants is studied as a function of the chemical nature of the polymers used as binders. The following five types of polymers are used:(1) hydroxy‐terminated polybutadiene (HTPB)(2) polypropyleneglycol (PPG)(3) polysulfide (PS)(4) polyesterpolyol (PO)(5) azidomethylmethyloxetane (AMMO) Experiments are conducted using differential thermal analysis (DTA), thermogravimetric analysis (TG), and burning rate analysis. The AP/PS propellant shows the highest burning rate and the AP/PO propellant shows the lowest burning rate within the propellants tested. Though the burning rate appears to be very dependent on the type of binder used, the characteristics of burning rate versus pressure cannot be correlated with the thermochemical data obtained by DTA and TG. The results of the photographic observation of the burning surface indicate that the formation of a melting layer of the binder reduces the burning rate due to the reduced reaction rate between the binder and the AP particles.     

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.     

Combustion Wave Structure of AP Composite Propellants

The combustion mechanism of ammonium perchlorate (AP) composite propellants were studied. The oxidizer-rich propellants tested were made with excess concentrations of AP particles. The pressure deflagration limit of propellant decreases with increasing the concentration of binder. The combustion wave consists of two reaction regions I and II: the region I is the zone of AP monopropellant flame and the region II is the zone of diffusion flame. The heat flux feedback from the gas phase to the burning surface increases as pressure increases, and the heat flux is responsible for the burning rate characteristics.     

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.     

Burning-rate behavior in aluminized wide-distribution AP composite propellants

Burning-rate behavior of aluminized, wide-distribution ammonium-perchlorate (AP), hydroxyl-terminated-polybutadiene (HTPB) binder composite propellants, both 2D laminates and 3D particulate propellants, is investigated experimentally. Very fine (2-μm) AP (FAP) is used at a high FAP/binder ratio (75/25) with either coarse (>200 μm) AP (CAP) particles (3D particulate propellants) or pressed AP slabs (simulating CAP particles in over-ventilated, 2D laminates). The results indicate that, while aluminum does not significantly alter the AP/binder flame structure, it can either increase the burning rate via radiative feedback or decrease it via inert heat-sink effects, depending on pressure (competing conductive heat feedback). Otherwise, the AP/binder flame structure is similar to that found previously for non-aluminized laminates, with minor differences. The FAP/HTPB-matrix burns with a one-dimensional premixed flame not hot enough to ignite aluminum, but hot enough to self-deflagrate if a modest amount of an external radiant flux (in the case considered, supplied by aluminum ignited downstream by the CAP/matrix flame) is present. The CAP/matrix interaction flame burns in either a split-diffusion or merged, partially premixed mode, depending on pressure and fuel-layer thickness. A correlation between the burningrate pressure exponent and the CAP/matrix flame-regime pressure dependence is found in terms of the Peclet number in accordance with a simple, conserved-scalar (mixture fraction) theory.     

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.     

Combustion of Propellants with Ammonium Dinitramide

This paper reports a series of experiments involving ammonium dinitramide (ADN), a new energetic oxidizer of potential use in composite solid propellants. The experiments include (a) self‐deflagration of pressed pellets of ADN; (b) combustion of sandwiches with ADN laminae on both sides of a binder lamina that is either “pure” or filled with particulate oxidizer and other additives; and, (c) combustion of propellants with a bimodal oxidizer size distribution, wherein, combustion of coarse ADN and fine AP (ammonium perchlorate) and vice versa were used, in addition to mixtures of coarse ADN and AP, fine ADN and AP, and all‐ADN or all‐AP formulations.     

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.     

AP-CMDB 推进剂稳态燃烧性能计算研究

建立了一个ＡＰ－ＣＭＤＢ推进剂稳态燃烧模型。该模型可用于ＡＰ－ＣＭＤＢ推进剂和经典双基推进剂燃速特性的模拟计算，其计算结果与文献值相符合，说明该模型是合理、可行的。ＡＰ－ＣＭＤＢ推进剂计算结果表明，ＡＰ粒径减小，ＡＰ含量增加，推进剂燃速升高；而含能粘结剂——ＤＢ母体的含能程度越高，即ＮＧ含量增加，或ＮＣ的硝化度加大，都有利于提高推进剂的燃速。     

Effect of tension of a composite propellant on its burning rate

Existing concepts of the effect of tensile strains on the burning rate of propellants are analyzed. It is demonstrated that the basic mechanism of increasing burning rate of composite propellants under tension is spalling of the binder from oxidizer particles, formation of an additional burning surface, and changes in the combustion-zone structure. To describe this effect, a rheological model of a composite solid propellant is developed, which takes into account separation of the binder from disperse particles of the fillers (oxidizers, coolants, metals, etc.). A criterion is found, which describes the difference between the propellant behavior under tension with spalling of the binder from the particles and the tension of the same material without the emergence of internal defects. A method of experimental determination of the number of defects arising in the propellant under tension, based on analyzing the tensile stress-strain diagram of the material, is proposed. A mathematical model of composite propellant combustion is developed, which takes into account separation of the binder from the oxidizer particles and formation of an additional burning surface. A correlation between the change in the burning rate of the propellant under tension and parameters of the propellant tensile diagram is found. A method for predicting the change in the burning rate of the propellant under tension on the basis of the propellant tensile diagram shape is developed.     

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.     

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.     

LOVA发射药点火燃烧性能

制备了含有两种不同黏结剂的低易损性发射药(即LOVA发射药),并应用点火燃烧模拟装置与密闭爆发器对其点火燃烧性能进行了研究。结果表明,LOVA发射药难点火,但在点火药中添加高氯酸铵后可有效改善LOVA发射药的点火性能。LOVA发射药燃烧具有燃速系数低、燃速压力指数高等特点。