Radiative Ignition of Fine‐Ammonium Perchlorate Composite Propellants

Radiative ignition of quasi‐homogeneous mixtures of ammonium perchlorate (AP) and hydroxyterminated polybutadiene (HTPB) binder has been investigated experimentally. Solid propellants consisting of fine AP (2 μm) and HTPB binder (~ 76/24% by mass) were ignited by CO₂ laser radiation. The lower boundary of a go/no‐go ignition map (minimum ignition time vs. heat flux) was obtained. Opacity was varied by adding carbon black up to 1% by mass. Ignition times ranged from 0.78 s to 0.076 s for incident fluxes ranging from 60 W/cm² to 400 W/cm². It was found that AP and HTPB are sufficiently strongly absorbing of 10.6 μm CO₂ laser radiation (absorption coefficient ≈250 cm⁻¹) so that the addition of carbon black in amounts typical of catalysts or opacitymodifying agents (up to 1%) would have only a small influence on radiative ignition times at 10.6 μm. A simple theoretical analysis indicated that the ignition time‐flux data are consistent with in‐depth absorption effects. Furthermore, this analysis showed that the assumption of surface absorption is not appropriate, even for this relatively opaque system. For broadband visible/near‐infrared radiation, such as from burning metal/oxide particle systems, the effects of in‐depth absorption would probably be even stronger.     

Effect of Coating of Ammonium Perchlorate with Fluorocarbon on Ballistic and Sensitivity Properties of AP/Al/HTPB Propellant

Fluorocarbon polymers are used to enhance thermal stability and electrostatic protection of composite propellant compositions. A precipitation technique has been developed to coat ammonium perchlorate (AP) using a copolymer of hexafluoropropylene and vinylidene fluoride (HFP‐VF) with the help of solvent‐counter solvent method. The coated AP has been used to prepare propellant compositions in different ratio based on hydroxyl terminated polybutadiene (HTPB), aluminium powder along with uncoated AP and studied for viscosity build‐up and visco‐elastic behaviour as well as mechanical, ballistic, thermal and sensitivity properties keeping 86% solid loading. The data on viscosity build‐up indicate that as the percentage of viton coated AP increases end of mix viscosity and viscosity build‐up increase accordingly. The mechanical properties data reveal that tensile strength and percentage elongation are found in increasing order. The burn rate of the composition also increases on higher percentage of HFP‐VF coated AP. The thermal stability of composition increases as the percentage of HFP‐VF coated AP increases. The data on sensitivity indicate that impact sensitivity decreases on increasing the percentage of HFP‐VF coated AP while no change is observed in friction sensitivity value.     

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.     

Multi‐Parameter Study of Nanoscale TiO2 and CeO2 Additives in Composite AP/HTPB Solid Propellants

A statistical Taguchi L8 matrix was used to conduct a multi‐parameter study of the use of nanoscale additives in composite solid propellants. The additives studied were TiO₂ (titania) and CeO₂ (ceria). The other parameters involved in the experiment were the oxidizer loading and distribution, additive percentage and size, additive size (nano‐scale or μm‐scale), and the mixing method. Four baseline propellants without additives were also produced for comparison. The propellants were tested from 3.45 to 13.78 MPa in a strand bomb, and burning rate curves were determined for all formulas. By analyzing the Taguchi matrix, the sensitivity of each parameter according to the pressure sensitivity and burning rate of the propellant was calculated. The dominant factors depend on whether the additive is needed for modifying the pressure index or the absolute value of the burning rate. In general, the effectiveness of the additives was most influenced by oxidizer percentage, oxidizer size distribution, and additive type. The amount of additive, mixing method, and additive size all had relatively minor impacts on the effectiveness of the additives.     

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%)。     

HTPB基PBX的模量与撞击感度的关系

为改善HTPB基PBX炸药的易损性,研究了炸药的模量与撞击感度之间的关系。通过改变端羟基聚丁二烯（HTPB）基PBX的固化参数与黏结剂的含量,制备了一系列具有不同模量的PBX,利用50％特性落高法对其撞击感度进行测试。结果表明,PBX的撞击感度随抗张模量和压缩模量的下降而降低。从理论上分析了影响撞击感度的模量因素和机理,认为通过调整PBX的力学性能可改善PBX炸药的机械撞击感度。     

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.     

端羟基液体聚丁二烯橡胶微观结构及其力学性能

通过FT—IR,HNMR,CNMR,GPC等方法,对相同牌号HTPB样品A和B的主链微观结构、羟基类型、环氧基团、官能度分布和固化物力学性能进行了对比,2个样品的主链微观结构、羟基类型、环氧基团含量基本一致,而官能度分布存在较大差异,由结果可得,HTPB官能度分布对其力学性能影响较大,二官能度为84．2％的样品A具有较好的力学性能,二官能度为676％的样品B具有相对较差的力学性能。     

HTPB聚氨酯材料的老化机理研究

通过加速老化试验,研究了HTPB／TDI／MAPO类聚氨酯材料的老化性能,探讨了其老化机理。实验结果显示,随老化时间的延长,HTPB胶片的表面硬度、凝胶百分数与相对交联密度均为先略微增加后明显降低的趋势。红外光谱测试结果表明,OH的伸缩振动峰强度降低,表明OH减少,这主要是由于贮存前期后固化的作用。P—N的相对吸光度值不断降低,说明P-N断裂。密封贮存条件下HTPB胶片的老化机理是后固化和降解断链。     

Conducting polymer based hybrid nano-composites for enhanced corrosion protective coatings

Hybrid composite coatings containing zinc oxide (ZnO) and polyaniline (PANI) as nano-additives dispersions were prepared with poly(vinyl acetate) (PVAc) as the major matrix. The steel plates dip-coated with these formulations were tested for corrosion protection by immersion in saline water over long periods. The Tafel plots for the determination of open circuit potential (OCP) and corrosion current (I_corr) were recorded. The coatings containing both ZnO and PANI showed improved corrosion resistance as compared to the single component coating. The I_corr values of PVAc–ZnO–PANI are found to be two-order magnitude lower than that of PVAc and PVAc–ZnO coatings. The results are explained on the basis of enhancement in barrier properties due to nano-particulate additives in PVAc–ZnO–PANI film together with the redox behaviour of PANI and protective oxide layer formation near the substrate.     

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。     

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.     

复合射孔器推进剂装药的损伤特性

以复合射孔器装填的AP-丁羟(HTPB/AP)复合推进剂为主要研究对象,通过不同载荷作用下的模拟试验,对装药试样进行模拟损伤.采用药柱密度测量技术和密闭爆发器试验,分析了试样的损伤程度,并对损伤装药的燃烧性能进行了研究.结果表明,HTPB/AP复合推进剂在不同载荷作用下,内部结构发生了微观变化及损伤,其损伤度由高到低依次为高速冲击、低速撞击、准静态压缩和高温冲击.试样的损伤程度越大,其燃烧性能的变化越大,其中经高速冲击和低速撞击的HTPB/AP复合推进剂的燃烧特性已转变为对流燃烧或压缩燃烧,在一定的外界约束条件下,很有可能产生燃烧转爆轰现象.     

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。     

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%。     

耐酸碱聚氨酯弹性体胶辊的研制

以端羟基聚丁二烯(HTPB)和聚四亚甲基醚二醇(PTMEG)为软段,2,4-甲苯二异氰酸酯(TDI-100)和3,3′-二氯-4,4′-二氨基二苯基甲烷(MOCA)为硬段,采用预聚体法制备了聚氨酯弹性体,讨论了不同软段比例对弹性体力学性能、耐酸碱性能及加工性能的影响。结果表明,软段中HTPB与PTMEG质量比为50∶50时,弹性体的综合性能较好,适合做耐酸碱胶辊的包覆胶。