Combustion of Aluminum Particles near the Burning Surface in AP/AN Composite Propellants

Aluminum (Al) particles are commonly used in ammonium perchlorate (AP) composite propellants of solid rockets for increasing performance. When propellants including Al particles burn, Al particles easily agglomerate on the burning surface of the propellant. The diameters of agglomerated Al particles are greater than those of mixed particles. The combustion efficiency of the propellant decreases with increasing burning time of the agglomerated Al particles. Therefore, it is important to observe how the agglomerated Al particles burn on the burning surface of AP composite propellant. A lot of researchers have studied Al agglomerate characteristics. Previous studies clarified the relation between the agglomerated Al particle diameter and luminous flame diameter around Al particles near the burning surface. The shapes of luminous flames around agglomerated Al particles are spherical or elliptical. This study evaluates the shapes of the luminous flame around agglomerated Al particles at a constant diameter or a different diameter. When the proportion of the luminous flame diameter (D_f) to the diameter of agglomerated Al particles (D₀) is 1.54–1.71 at a constant D₀, the luminous flames are almost perfectly spherical. Otherwise, the luminous flames are elliptical at a constant D₀. Furthermore, when D_f/D₀ is close to the mean value, the luminous flame is more spherical than elliptical at different D₀. The evaporation rate and the burning rate of Al vapor are inversely proportional to D₀. The oxidation gas temperatures were changed and the activation energy of Al vapor was obtained as 39.2 kJ mol⁻¹.     

Thermal Decomposition of AMMO/AP Composite Propellants

Thermal decomposition of AMMO/AP composite propellants was studied by DTA, TGA and DSC in helium atmosphere. The effects of accelerated aging at 347 K for 370 days on decomposition kinetics were also measured. AMMO/AP propellant showed two different decomposition steps, which were mainly the AMMO binder decomposed region and the reaction of AP dominated region. These regions were separated at around 20 % weight loss point at the condition used in this study. AMMO binder decomposition and AP decomposition were strongly related each other. The heat generated by the AMMO binder decomposition initiated and accelerated the thermal decomposition of AP. Although both Fe₂O₃ and CFe activated the thermal decomposition of AMMO/AP propellants, CFe mainly accelerated the decomposition of AMMO binder and Fe₂O₃ catalyzed the AP reactions which consisted of the AP decomposition and the reaction between decomposed AP and decomposed AMMO binder. AMMO/AP composite propellants were thermally stable even after aging at 347 K for 370 days.     

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.     

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。     

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.     

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.     

Mechanical Properties of Composite AP/HTPB Propellants Containing Novel Titania Nanoparticles

Modern chemical synthesis techniques have allowed for improved incorporation of nano‐scale additives into solid propellants. Various methods were implemented to incorporate titania nanoparticles into three representative ammonium perchlorate composite propellants (APCP), and the mechanical properties of each formulation were tested and compared to those of an analogous baseline. Advanced imaging techniques were applied to all particle synthesis methods to characterize particle size and particle network type and size. Uniaxial tensile testing was performed to measure propellant ultimate strength, ductility, and elastic modulus. In general, the addition of nano‐titania additives to the propellant decreased propellant strength and modulus, but improved ductility. Propellant formulations containing in‐situ titania exhibited an increase in ductility of 11 %, 286 %, and 186 % with a corresponding reduction in strength of 82 %, 52 %, and 17 % over analogous baselines. These trends corresponded to a simultaneous decrease in propellant density, indicating that when implementing nano‐sized additives, care must be taken to monitor the effect of the altered manufacturing techniques on propellant physical properties in addition to just monitoring burning rates. Tailoring of propellant manufacturing procedures and the addition of Tepanol bonding agent to an in‐situ APCP formulation fully recovered the propellant density and ultimate strength while retaining the enhanced ductility.     

Studies on Aluminum Agglomeration and Combustion in Catalyzed Composite Propellants

Combustion, Explosion, and Shock Waves - Composite propellants are tested using the quench particle collection bomb (QPCB) for the pressure ranging from 2 to 8 MPa to estimate the particle...     

Development of MTV Compositions as Igniter for HTPB/AP Based Composite Propellants

MTV compositions were prepared by keeping the magnesium/Teflon ratio constant and increasing the Viton content of the mixture up to 14% by an increment of 2% to investigate the effect of binder content on the heat of explosion, which is found to increase with the increasing Viton percentage as the magnesium content concomitantly goes down toward the stoichiometric value. In the second part of the study, fuel-rich MTV compositions were prepared by changing the magnesium content and keeping the Viton fraction constant at a specific value to investigate the effect of magnesium content on the heat of explosion and combustion characteristics. The observed general trend is that the heat of explosion of MTV compositions decreases as the magnesium content increases. All the MTV compositions were tested in a closed vessel to measure the maximum pressure achieved and the rate of reaching this pressure. The ignition performance of three selected MTV compositions was examined in 2.75 inch rocket motor by using the same charge of igniter and the same HTPB/AP composite propellant of the equal amount in each test. Two of them have excellent ignition performance and, therefore, can be used as igniter for the HTPB/AP based composite rocket propellants.     

Mechanism of Catalytic Effects on AMMO/HMX Composite Propellants Combustion Rates

Thermal decomposition and the burning properties of AMMO/HMX propellants have been investigated. The heat generated by the AMMO decomposition initiated and accelerated the thermal decomposition of HMX, and the reaction between decomposed AMMO and HMX depended upon the heating rate. The rate determining step of the reaction path was different in higher and lower heating rate conditions. 2,2-bis(ethylferrocenyl)propane (CFe) and copper chromite (CuC) significantly altered the mechanisms of the thermal decomposition and the burning properties. CFe showed an increase in burning rate with a slight increase in burning rate exponent. However, CuC yielded high values for the burning rate exponent. The combined additive yielded the highest burning rate with the lowest burning rate exponent. The influence of CuC on the burning rate exponent disappeared by the combination with CFe. Though CFe and the combination additive improved the ignitability of the propellants, the propellant with CuC was difficult to ignite because of the relatively small quantity of heat feedback and/or heat released by the decomposition.     

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.     

HTPB/AP复合推进剂冲击波点火实验研究

根据增效射孔器的实际作用,以AP-丁羟（HTPB/AP）复合推进剂为研究对象,利用隔板试验研究了冲击波对AP-丁羟复合推进剂的点火性能,结果表明,合理控制冲击波强度能够使AP-丁羟复合推进剂可靠点燃,并为其它推进剂的点火提供了一种新方法.     

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。     

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.     

Study on Unsteady Combustion Behaviors of AP/HTPB Base‐Bleed Propellants under Transient Depressurization Conditions

As the base‐bleed projectile flies out of the muzzle, the environmental pressure in the base‐bleed combustion chamber suddenly decreases and AP/HTPB base‐bleed propellant suffers intense unsteady combustion. To further study the unsteady combustion characteristics of base‐bleed propellants, a semi‐closed bomb as was designed experimental device and transient depressurization conditions of the muzzle were simulated. Measurements of the transient combustion characteristics of the base‐bleed propellant under high depressurization rate were carried out by using a high speed digital camera system. In the experiments, the combustion chamber pressure of the semi‐closed bomb was controlled from 20 to 90 MPa and the depressurization rate was controlled from 400 to1.12×10⁴ MPa s⁻¹. The experimental results indicate that, the out‐of‐phase blowing effect is intense under rapid depressurization condition, leading to the reaction layer thickened. The thermal feedback to the solid surface decreases and thus the combustion reaction of gas phase is so difficult to maintain that it begins to extinguish. However, the thermal decomposition of the solid phase is still continuing and a yellow fog can be observed above the combustion chamber nozzle. Depending on the maximum pressure in the combustion chamber and depressurization rate, the transient combustion behavior of AP/HTPB base‐bleed propellant displays three patterns, i.e., automatic reignition, oscillating combustion (a critical type) and permanent extinguishment. Three unsteady combustion behaviors are preliminarily analyzed based on the thermal feedback. If the initial pressure in the combustion chamber before depressurization is larger or the depressurization rate is smaller, the base‐bleed propellant tends to automatically reignite earlier and the combustion process is more stable.     

铝/有机氟化物复合物对含铝HTPB推进剂燃烧性能的影响

为研究有机氟化物(OF)对含铝HTPB固体推进剂燃烧性能的影响,采用球磨法制备了纳米和微米铝/有机氟化物复合物(nmAl/OF和μmAl/OF),将其作为复合添加剂替代微米铝粉加入HTPB推进剂中,并考察其对推进剂燃烧性能的影响。采用SEM、TEM、粒度分析等对nmAl/OF和μmAl/OF复合物及推进剂凝聚相燃烧产物进行了表征。结果表明,nmAl/OF和μmAl/OF复合物有不同的结合状态;添加OF、nmAl/OF和μmAl/OF后,推进剂的爆热值下降约2%;添加nmAl/OF的推进剂配方燃速最低,在3MPa时仅为6.28mm/s,添加OF和μmAl/OF体系的推进剂燃速压强指数相比于原配方降低约20%;添加nmAl/OF的推进剂配方凝聚相燃烧产物粒度(D_(50))比原配方降低约47%。     

Burning Characteristics of AP/HTPB Composite Propellants Prepared with Fine Porous or Fine Hollow Ammonium Perchlorate

Fine porous and hollow ammonium perchlorate (AP) particles were prepared by the spray‐drying method. Propellants prepared with porous or hollow AP were found to have bubble contamination. The bubble in the propellant appeared inside the porous and hollow AP particles because the voids in porous and hollow AP cannot be completely filled with HTPB. The relationship between the burning rate and the weight mean diameter, D_w, and the specific surface area, S_w, is divided into two regions. The burning rate was almost constant above the critical D_w and increased with decreasing D_w below that. The burning rate was almost constant below the critical S_w and increased with increasing S_w above that. These critical points did not depend on the voids in the AP particles. The burning rate of the propellant prepared with spherical AP was dependent on D_w and S_w. The burning rates of the propellants prepared with porous or hollow AP were not associated with D_w or S_w alone and were greater than that of the propellant prepared with spherical AP at a constant D_w or S_w. The voids in porous and hollow AP particles thus had a positive effect on the burning rate.     

程序控制开裂棒状发射药的燃烧性能

应用密闭爆发器试验，对程序控制开裂棒状（ＰＳＳ）发射药的燃烧性能进行了研究。发现采用不同端封剂的ＰＳＳ发射药的燃烧性能有着明显的差异。研究结果表明，提高端封层的抗燃气冲击性能是研制ＰＳＳ发射药成功的关键之一。     

Experimental study of Double-Base Propellants Combustion Mechanisms

Experimental results about r_b(P) laws of double-base propellants are presented. The influence of many parameters (calorific potential, fabrication process, additives) is studied. With surface structure examination, we show that the first super-rate (P < 100 bar) is in relation with the presence of a carbon layer which increases chemical reactions. The second super-rate (200 bar < P < 400 bar), more physical than chemical, is in relation with the presence of globules (probably PbO) which increase the thermal conductivity near the propellant surface.     

Combustion of HMX-CMDB Propellants (I)

The combustion wave structure of HMX-CMDB (composite modified double-base) propellants was studied in order to elucidate the gas phase reaction mechanism and to understand the burning rate characteristics. Experiments were conducted to determine the thickness of the reaction zone, gaseous products in the dark zone, and the temperature profile in the combustion waves. The reaction rate in the dark zone is increased by the addition of HMX. This is caused by the equivalence ratio of the oxidizer/fuel in the dark zone shifting towards a stoichiometric ratio when HMX is added. However, the reaction rate in the fizz zone and the heat feedback from the gas phase to the burning surface is decreased by the addition of HMX. Thus, the burning rate of HMX-CMDB propellants decreases when HMX is mixed within double-base propellants.