含微米级AP的HTPB推进剂工艺性能和力学性能

制备了含微米级AP(质量分数大于50%)的HTPB推进剂药浆和标准试件,利用流变仪测试了+20℃和-40℃时药浆的表现黏度,用材料试验机测试了标准试件的力学性能,讨论了增塑比、AP粒度级配、键合剂等对HTPB推进剂工艺性能和力学性能的影响。结果表明,当增塑比为0.42、AP粒度级配采用25%的120μm AP、30%的6~8μm AP和20%的1μm AP时,推进剂样品6h的表观黏度为1 267Pa·s,低温延伸率达到38%。     

丁羟复合推进剂的辐射点火

采用CO2激光点火装置,对丁羟复合推进剂的点火过程进行了实验研究,利用描述固体推进剂物化现象的一维传热模型对复合推进剂的辐射点火特性进行了理论分析。通过最小二乘法拟合实验数据得到了丁羟复合推进剂的点火准则。结果表明,丁羟复合推进剂的点火过程主要包括惰性加热及气相点火过程,惰性加热时间和点火延迟时间随热流密度的增大而减小,且随着热流密度的增大,热流密度的影响逐渐降低。固相传热数学模型能够比较准确地描述复合推进剂的辐射点火特性。     

Aging of HTPB/Al/AP Rocket Propellant Formulations Investigated by DMA Measurements

Three HTPB‐based rocket propellant formulations containing ammonium perchlorate and aluminum particles, with different aluminum content and particle size, have been manufactured. The study has focused on the change of mechanical properties with aging time by using dynamic mechanical analysis (DMA). Therefore, propellant formulations underwent an accelerated aging program, in air (RH<10 %), between 60 °C and 90 °C with aging time adjusted to a thermal equivalent load of 15 to 20 years at 25 °C. DMA investigations revealed distinct changes in the shape of the loss factor curve. These curves were modeled with three exponentially modified Gaussian (EMG) functions in order to get the molecular interpretation of the involved aging phenomena by separating the binder fractions with different mobility. Aging of propellant formulations can be followed by considering only two parameters: the areas of the second and third loss factor transition peaks (A₂, A₃), and the corresponding maximum temperature values of the assigned Gauss peaks (Tc₂, Tc₃).     

Comparison of Commercially Available and Synthesized Titania Nano‐Additives in Composite HTPB/AP Propellant

This study presents a comparison of commercially available titania nano‐particles produced using electric wire explosion with nano‐particles manufactured by the authors using a sol‐gel synthesis process. For the present study, 20‐nm titania was purchased off‐the‐shelf. It was determined to be rough spheres of 20 nm forming large, micron‐sized agglomerates, whereas particles synthesized using the sol‐gel process were found to be fundamentally 10 nm but with sub‐micron agglomerations thereof. The nano‐titania was added to 80% AP monomodal propellants at 0.3% and 1.0% by mass. Additional, 85% bimodal‐AP mixtures were made, comparing commercial titania to the laboratory‐synthesized particles at 1.0% by mass. Another set of samples compared a method of pre‐mixing the synthesized additives directly into the binder material at 0.3% by mass of laboratory titania; two additional pre‐mixed titania batches at 0.5% by mass were doped with either Fe or Cu into the nanocrystals. All propellants were tested up to 13.8 MPa at 3.8 MPa increments. Dry powder laboratory additives show a 60‐to‐100% increase in burning rate over the baseline samples with no catalyst and a 20‐to‐30% increase over the commercial nano‐particles. Pre‐mixed additives were found to produce similar burning rate increases but with lower concentrations required. This latest generation of particle synthesis techniques was further demonstrated in this study to have great potential for future propellant catalyst development.     

AP/HTPB复合推进剂用纳米Co粉的制备

以CoCl_2·H_2O和水合联氨(N_2H_4·H_2O)为主要原料,采用化学还原法制备了纳米Co粉.在不同工艺条件下制备了树枝状纳米Co粉和球形纳米Co粉,用TEM和XRD对产物进行了表征,同时用DTA测试了加入球形纳米Co粉后AP的热分解性能.结果表明,反应介质的黏度和分散剂性质对纳米Co粉粒度及形貌影响较大,在最佳工艺条件下制备了颗粒尺寸均匀、粒度为50~60 nm的球形纳米Co粉;球形纳米Co粉能使AP热分解反应的高温分解峰温度显著下降;添加质量分数2%的球形纳米Co粉,复合推进剂的燃速明显提高,压力指数大幅降低.     

Numerical Simulation of Quenched Combustion Model for AP/HTPB Propellant under Transient Depressurization

In order to study the out‐of‐phase blowing effect of ammonium perchlorate/hydroxyl terminated polybutadiene (AP/HTPB) under transient depressurization, a two‐dimensional periodic sandwich model of AP/HTPB sandwich unsteady combustion was established. The gas‐solid two‐step total reaction was used to couple the gas‐solid boundary layer, and the AP/HTPB step‐down temperature criterion was applied. The numerical simulation comparative analysis under the initial combustion pressure 3.5 MPa∼10 MPa and the initial depressurization rate of 1000 MPa/s∼2000 MPa/s was experimented. The results show that under the condition of initial combustion pressure of 3.5 MPa and pressure reduction rate of 1000 MPa/s, the formation of narrow diffusion chemical reaction zone appears in the initial stage of depressurization; when the combustion pressure drops to about 1.7 MPa, the flame appears dual characteristics: diffusion and premixed combustion; when the pressure dropped to 0.1 MPa, the flame is premixed combustion. AP(g) is the main factor causing the out‐of‐phase blowing effect. During the initial stage of combustion, AP(g) decomposes rapidly and its decomposition product is close to the combustion surface; with the rapid decrease of pressure, the gas‐phase heat feedback decreases, leading to the decrease of AP(g) decomposition rate and AP(g) diffusion to the gas phase, which is the initial phase of out‐of‐phase blowing effect; when the gas phase heat feedback reduced and the temperature is below 750 K, the decomposition of AP(g) is stopped and the undecomposed AP(g) is further diffused to the gas phase region, which exacerbates the out‐of‐phase blowing effect, leading to the extinguishment of AP/HTPB. The unsteady combustion flame extinction time increases with the initial combustion pressure, and decreases with the initial depressurization rate.     

HTPB/Al/AP/RDX复合推进剂组元之间相互作用研究

为了探索HTPB/Al/AP/RDX复合推进剂组元之间的相互作用,用DSC和TG-DTG方法以及分解反应动力学计算研究了递增组元的4个混合体系(包括HTPB黏合剂体系、HTPB/Al、HTPB/Al/AP和HTPB/Al/AP/RDX推进剂体系)中各组元之间的相互作用。结果表明,DTG峰温以及反应速率常数k可以表征各组元之间的相互作用,其DSC和TG过程可以分为3个阶段;除Al外,各组元之间存在相互作用,各阶段的质量损失测定值与按组分含量计算的加合值吻合得相当好,表明各组元并没有明显的跨阶段分解;AP与HTPB黏合剂的分解温度区间接近或部分重叠,在HTPB/Al/AP和HTPB/Al/AP/RDX的混合体系中发生了强烈氧化还原作用:四组元体系中RDX在200℃及220℃的速率常数k分别为1.53和6.81s-1,均大于单质RDX在同一温度下的速率常数1.33×10-6和1.06×10-5s-1,说明AP可以加速RDX的分解,但RDX对AP或(AP+HTPB)分解的影响呈现复杂的情况,由于HTPB/Al/AP和HTPB/Al/AP/RDX两体系中AP与HTPB的共同分解过程中存在“等动力学点”(308.0℃),温度低于此点时(AP+HTPB)分解速率常数k因RDX存在而下降,而当温度高于此点时则该k值因RDX存在而增大。通过RDX分解机理解释了存在这种现象的原因。     

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.     

超声空化-表面活性剂水溶法提取RDX/Al/AP/HTPB炸药中的AP

为了对RDX/Al/AP/HTPB炸药的有效成分进行分离回收,研究了以超声空化-表面活性剂水溶法提取RDX/Al/AP/HTPB炸药中高氯酸铵(AP)的分离工艺,探讨了各工艺参数对AP提取率的影响。结果表明,表面活性剂浓度、提取时间和超声频率是影响AP提取率的主要因素,表面活性剂种类为次要因素,料液质量比和提取次数对AP提取率的影响很小。最佳工艺条件为:室温,提取时间40min,料液质量比1∶3,提取次数1次,超声功率3.0kW,表面活性剂为吐温80(质量分数2.0%)。     

溶胀/溶解法回收HTPB推进剂中AP组分的实验研究

采用溶胀/溶解法回收报废HTPB推进剂中的AP。研究了浸取时间、浸取温度、四氢呋喃质量分数、液料比(四氢呋喃溶液体积与HTPB推进剂的质量比)、试样厚度及搅拌速率对AP回收率的影响。通过扫描电镜、X射线能谱仪对回收得到的AP进行表征,并对其纯度进行了检测。结果表明,AP的最佳回收工艺参数为:浸取时间6h、浸取温度60℃、四氢呋喃质量分数80%、液料比10∶1(mL/g)、试样厚度3mm、搅拌速率500r/min。其中,浸取时间、浸取温度和四氢呋喃质量分数对AP回收率的影响较大。在最佳工艺条件下,AP的回收率为95.0%,纯度为96.1%,表明此方法可用于报废HTPB推进剂中AP组分的回收。     

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。     

新型高氯酸铵替代物对固体推进剂能量性能的影响

为考察新型高氯酸铵(AP)替代物二硝酰基胺铵(ADNA)、四硝基六氢嘧啶(DNNC)、六硝基-二氮杂环辛烷(HCO)及二硝酰胺基二硝基乙撑二铵(ADNDNE)对固体推进剂能量性能的贡献水平,采用能量计算星程序5.0版,计算了4种替代物对CMDB、HTPB、NEPE、p(BAMO-AMMO)推进剂能量性能的影响。结果表明,4种替代物取代4种配方中的AP都降低了推进剂排气羽流的红外辐射性能;ADNA使4种配方体系的标准理论比冲都增加;如果设计氧系数较高的配方体系,DNNC、HCO及ADNDNE都将对能量性能产生增益。     

组分对高能HTPB推进剂燃烧性能和力学性能的影响

通过调整氧化剂AP粒径与含量、键合剂及R值，研究了固体质量分数为90％的HTPB推进剂的燃烧性能和力学性能。结果表明，在HTPB推进剂能量性能得到提高的同时，推进剂的燃烧性能和力学性能也得到了较好的保证。高固体含量下HTPB推进剂的燃烧和力学性能随配方调节呈现出较为明显的规律。推进剂的燃烧性能稳定，燃速和压力指数可调，压力指数控制在0．30～0．40；分别测定了高温（60℃）、常温（20℃）和低温（-40℃）力学性能，高温、低温和常温下的拉伸强度一般均大于1．0MPa，低温延伸率最高可达74．7％。     

丁羟推进剂/衬层粘接界面材料力学性能研究

比较了目前测试推进剂/衬层粘接界面性能的方法。针对丁羟推进剂/衬层粘接界面,采用国内外关于推进剂与金属材料粘接界面性能的微型拉伸试验方法,设计并开展了微型拉伸试验,得出该推进剂材料在粘接界面处的受影响区域范围及相应的材料性能特征。     

AP/Al/SMX/HTPB四组元推进剂能量特性的理论研究

采用推进剂性能评估软件(PEP),计算和比较了2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯(SMX)和HMX取代高氯酸铵/铝粉/丁羟黏合剂(AP/Al/HTPB)推进剂中AP对配方能量性能的影响。用高温化学平衡计算代码模拟计算了AP/Al/SMX/HTPB和AP/Al/HMX/HTPB复合固体推进剂的能量和标准发动机工作过程。结果表明,与HMX相比,SMX能在更大的配比范围内提高HTPB推进剂的能量水平。在质量分数14%HTPB、18%Al的配方中,SMX能有效将推进剂的平衡流比冲提高到2 622.5N·s/kg,比HTPB三组元能量优化配方高27.5N·s/kg。在质量分数14%HTPB、15%Al的配方中,SMX取代AP后,比冲最高可达2 634.2N·s/kg,比HTPB三组元能量优化配方高39.2N·s/kg。在质量分数15%Al、HTPB质量分数为12%和10%的配方中,SMX质量分数可分别达到45%和65%;最高比冲可分别达到2 652.9和2 679.3N·s/kg,比HTPB三组元能量优化配方分别高57.9和84.3N·s/kg。在不含Al或Al含量很低的配方中,SMX可取代全部AP。     

储氢合金/AP/HTPB推进剂的热分解性能

采用TG-DTG、DSC以及动力学分析方法研究了储氢合金/AP/HTPB推进剂的热分解性能。结果表明,相对于Al/AP/HTPB推进剂,储氢合金/AP/HTPB推进剂的热分解温度降低,放热量提高;A20/AP/HTPB推进剂的凝聚相反应程度提高2.44%,第二、三温区的热分解活化能(Kissinger法)分别降低4.06%和22.63%;A30/AP/HTPB推进剂的凝聚相反应程度提高10.61%,第二、三温区的热分解活化能(Kissinger法)分别降低30.89%和38.87%。储氢合金对AP/HTPB推进剂的热分解有催化作用,并且该催化作用随着储氢合金中Mg0.45Ni0.05B0.5Hx含量的增加而增强。     

湿度对丁羟推进剂及其粘接性能的影响研究

固体火箭发动机燃烧室内绝热层、人工脱黏层及推进剂药柱,均为高分子材料复合体系。在成型及贮存过程中,湿度是影响丁羟推进剂药柱性能及各界面的联合粘接强度的首要因素。探讨了绝热层、衬层及推进剂药柱在不同环境湿度下的吸湿特性,通过模拟实际生产过程的环境湿度,研究了丁羟推进剂药柱性能及各界面的联合粘接强度变化状况。     

亚大气压下AP/HTPB微尺度稳态燃烧的数值模拟

为研究亚大气压下高氯酸铵/端羟基聚丁二烯(AP/HTPB)的燃烧特性,采用三步反应动力学机理,建立二维三明治模型,耦合气固两相;对20~80kPa下AP/HTPB的微尺度燃烧进行模拟,并与高压下(4MPa)AP/HTPB燃烧特性差异进行对比。结果表明,亚大气压下BDP模型中第一步反应靠近燃面,放热量较大,在AP/HTPB推进剂燃烧过程中占主导地位;燃烧环境压强不同,导致火焰的特性不同,亚大气压下火焰中扩散与混合过程共存,高压下为扩散火焰;相比于高压,亚大气压火焰离燃面远,面积大;由于高低压下放热区域及放热率差异导致气固相温度分布不同,从而影响燃面形状,亚大气压下AP与HTPB交界处相对于整个燃面突出,而高压下交界处相对于整个燃面凹陷。     

两种新型键合剂改善 AP/HTPB 推进剂力学性能的作用效果

通过单轴拉伸试验，研究了两种新型键合剂改善ＡＰ／ＨＴＰＢ复合固体推进剂力学性能的作用效果，及其对推进剂工艺性能的影响。研究表明，这两种新型键合剂能够明显地改善推进剂的力学性能，且推进剂的工艺性能良好。     

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.