含团聚硼粉富燃料推进剂一次燃烧模型的建立

为研究团聚硼粉对富燃料推进剂燃烧过程中能量释放和燃速特性的影响,结合实验分析建立了基于BDP模型的含团聚硼粉富燃料推进剂一次燃烧的物理和数学模型.该物理模型中,燃烧表面由团聚硼粉、AP和黏合剂的聚集区两部分组成,气相区形成了AP火焰和FF(终焰)聚集区,团聚硼粉中团聚剂参与了PF(初焰)和FF.在假设团聚硼粉为惰性物质基础上,建立了该推进剂的数学燃烧模型.通过AP/HTPB体系、团聚硼粉/AP/HTPB体系的简化与计算,推导出燃速公式中SAP/S的表达式.该模型充分考虑了团聚硼粉体积分数ζ1对推进剂燃面的影响,将硼粉的体积因素引入含硼富燃料推进剂的数学燃烧模型公式,该模型合理解释了这种推进剂的主要燃烧特性.     

团聚硼对富燃料推进剂燃速的影响

通过调节黏合剂种类和团聚工艺,采用于法硼团聚工艺制取球形度良好、粒径为0．105～0．19mm的团聚硼粒子,并制得硼质量分数32％、热值约32MJ／kg、工艺性能良好的含硼富燃料推进剂;采用靶线法测试含硼富燃推进剂的燃速及压强指数,并测试不同AP粒度级配、镁铝合金粒径以及团聚硼粒径对富燃推进剂燃速的影响。结果表明,减小AP粒度及团聚硼粒径、增加超细AP含量和固体组分含量,可大大改善含硼富燃推进剂的燃烧性能。而镁铝合金粒径对推进剂的燃烧性能基本没有影响。     

硼粉含量对Mg/PTFE富燃料推进剂性能的影响

为研究硼粉含量对镁/聚四氟乙烯(Mg/PTFE)富燃料推进剂性能的影响,采用混合模压成型工艺制备了7种不同硼粉含量的Mg/PTFE推进剂药柱。用红外测温仪、TG-DTA、量热仪分别测试其燃烧性能、热分解性能和爆热,并测试了其机械感度。结果表明,加入硼粉后,推进剂的燃烧性能明显改善,硼粉质量分数为15%时,线性燃速和质量燃速达到最高;当硼粉质量分数为20%时,燃烧温度达到最高;随着硼粉含量的增加,爆热稍微降低,完全燃烧热随着硼粉含量的增加而增大;当硼粉质量分数为10%时,高温放热峰温度降低128℃,撞击感度和摩擦感度达到最高值。     

含硼富燃料推进剂的技术现状与发展趋势

综述了国内外在硼粒子的点火、燃烧性能,硼粉的包覆、团聚造粒技术,硼粉处理对配方性能的影响,含硼富燃料推进剂配方及性能测试表征手段等方面的研究进展。总结了国内外含硼富燃料推进剂工程化应用的现状和存在的差距。     

RDX对含硼富燃料推进剂一次燃烧产物组分影响的计算研究

为了研究黑索今(RDX)对含硼富燃料推进剂一次燃烧产物组分的影响,用吉布斯最小自由能法计算了5种推进剂配方的一次燃烧产物组分,并通过测试燃烧产物中的总硼含量对热力学计算结果进行了验证。结果表明,采用最小自由能法计算含硼富燃料推进剂的一次燃烧产物组分,其结果准确、可靠;当含硼富燃料推进剂中RDX含量增加时,一次燃烧产物中B_4C和B_2O_3含量减少、C和BN含量增加,且一次燃烧温度也升高;提高一次燃烧压强可提高硼的氧化率、降低B_4C的生成量,有效提高一次燃烧温度,因此提高一次燃烧压强有助于提高含硼富燃料推进剂的二次燃烧效率。     

提高含硼富燃料推进剂能量的技术途径

为提高含硼推进剂的能量,在确定基础配方的情况下,采用热力学计算软件,计算了含硼富燃料推进剂的理论能量,讨论了提高含硼富燃料推进剂能量的技术途径。计算结果表明,当推进剂中其他组分含量一定时,增加硼含量、减少AP含量或以HTPB代替BAM O/THF黏合剂,可提高含硼富燃料推进剂的比冲。发动机试验结果表明,在配方中添加质量分数5%~8%的镁粉,推进剂的一次喷射效率大于98%,细粒度硼粉和F类化合物可以提高该推进剂的比冲,而添加F 3化合物可将比冲提高到9 502N.s.kg-1。     

团聚硼颗粒在HTPB富燃料推进剂中的流变特性

为了探索球形团聚硼颗粒的制备效果,对端羟基聚丁二烯(HTPB)黏合剂、不同类型的团聚硼颗粒与HTPB黏合剂以一定质量配比形成的悬浮液,以及含团聚硼颗粒HTPB富燃料推进剂流变特性进行了对比研究。结果表明,HTPB黏合剂的表观黏度随温度的升高而降低,最终趋于某一定值;在一定温度下,无定形硼粉经团聚改性后,团聚硼颗粒与HTPB形成悬浮液的表观黏度和屈服值较团聚前降低,且两者均随时间的增加而增加;采用含团聚硼颗粒的富燃料推进剂药浆的流变特性大大改善,有利于含硼富燃料推进剂能量的提高和燃烧性能的改善。     

含AP包覆硼的富燃推进剂燃烧机理研究

通过微热电偶测温和火焰单幅照相技术测试了含硼富燃料推进剂燃烧波温度分布及燃烧火焰结构;用扫描电镜对熄火表面形貌进行了观察,并通过能谱仪进行局部元素分析;对DSC曲线进行积分,得到推进剂的凝相放热量;测量推进剂燃烧的爆热和低压燃速,获得了其低压燃烧特性和一次燃烧放热情况。结果表明,含AP包覆硼的推进剂燃烧更剧烈,推进剂的绝热火焰温度更高,AP包覆硼提高了含硼富燃料推进剂的凝相放热、爆热和低压燃速。初步确定了该类推进剂的燃烧过程,为建立含硼富燃料推进剂燃烧物理模型提供了依据。     

含硼固体推进剂燃烧残渣中三氧化二硼和碳含量测定及燃烧机理研究

为了研究含硼富燃料固体推进剂燃烧机理,对3种配方的不同批次含硼富燃料固体推进剂在不同压强的燃速进行了测试,利用化学分析法对其燃烧残渣中B2O3和C含量也进行了测定。结果表明,硼粒子表面的B2O3延缓了硼粒子的进一步燃烧,因此残渣中B2O3含量较低;随着氮气压强增高,残渣中B2O3含量降低,而C含量、B2O3与C总含量升高;随着推进剂配方中镁含量增高,残渣中B2O3含量降低,C含量先升后降,B2O3和C总含量则降低。     

B/Fe_2O_3/NC复合物的制备及其对HTPB/AP推进剂性能的影响

为改善硼粉(B)的性能和纳米氧化铁(Fe_2O_3)在固体推进剂中的分散性,用静电喷雾法制备了B/Fe_2O_3/NC复合物,采用扫描电镜(SEM)表征了复合物的表面形貌,用TG-DSC分析了复合物的热性能及其对HTPB/AP推进剂热性能的影响,并用燃速测试和密闭爆发器实验研究了该复合物对HTPB/AP推进剂燃烧性能的影响。结果表明,所制备的B/Fe_2O_3/NC复合物均以团聚体的形式存在,复合物中B的活性提高,其氧化反应温度提前;团聚硼粉对HTPB/AP推进剂燃烧性能的改善效果明显优于原料硼粉;加入Fe_2O_3后,会进一步改善含硼推进剂的燃烧性能,而且随Fe_2O_3含量的增加,在密闭爆发器中HTPB/AP推进剂达到最高压力所需的时间逐渐减小。当Fe_2O_3的质量分数为8%时,推进剂在常压空气中的燃速最大,为不添加B/Fe_2O_3/NC复合物的HTPB/AP推进剂的2.77倍。B/Fe_2O_3/NC复合物对推进剂的热分解具有一定催化作用,且随Fe_2O_3含量的增加催化作用增强。     

Preparation and Properties of Boron‐Based Nano‐B/NiO Thermite

Boron particles have several major burning problems, such as incomplete combustion, poor ignitability, and a complex burning process in solid propellants. It is documented that the low ignitability and combustion efficiency of boron are caused by the oxidation of its surface. In order to improve the combustion efficiency of boron particles, a precipitation method was employed to prepare nanometer‐sized NiO and coat it on boron particles. The morphology and coating results of the B/NiO nanocomposite thermite were characterized using different approaches such as SEM, X‐ray Diffraction (XRD), and EDS. The results indicated that the boron particles were well distributed and coated completely by nanocomposite NiO. The B/NiO nanocomposite thermite reaction process was tested by TG‐DTA. The results showed that the reaction temperature of B/NiO particles is about 30 °C lower than that of boron particles. The B/NiO thermite and boron powder were added to Mg/PTFE propellant to be measured for their respective combustion performance. The results showed that the burning rate of the B/NiO‐Mg/PTFE propellant increased by 22.8–25.2 %, mass burning rate by 26.7–30.8 %, and combustion temperature increased by 8–56 °C compared to the B‐Mg/PTFE propellant. The above results indicate that NiO coating of boron particles has a significant effect on the combustion behavior and increases the combustion performance of the propellant compared with uncoated particles.     

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.     

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.     

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。     

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.     

ACP对无烟改性双基推进剂能量和燃烧性能的影响

含ACP的无烟改性双基推进剂能量特性理论计算表明,ACP对推进剂的能量影响较小。研究了不同工艺对含ACP无烟改性双基推进剂燃烧性能的影响。实验结果表明,ACP对压伸工艺制备的推进剂燃速没有显著提高,但能大幅度地提高浇铸无烟改性双基推进剂的燃速。分析了ACP提高无烟改性双基推进剂燃速的作用机理,认为ACP可增加燃烧表面积和热量向燃烧表面积的反馈,使推进剂的燃速大增。