Insensitive energetic microspheres DAAF/RDX fabricated by facile molecular self-assembly

Insensitive energetic materials are promising in the defense weapons field. However, energetic materials still suffer from great challenges and the concern about their safety limits their utilization. In this work, insensitive energetic explosive 3,3′-diamino-4,4′-azoxyfurazan/hexahydro-1,3,5-trinitro-1,3,5-triazine (DAAF/RDX) microspheres were fabricated by self-assembly method. Rod-like DAAF/RDX was prepared by mechanical ball milling for comparison. DAAF/RDX composites with different mass ratios (90:10, 80:20, and 70:30) were obtained. The morphologies and structures of as-obtained DAAF/RDX composites were characterized by scanning electron microscopy (SEM), powder x-ray diffraction (PXRD) and fourier transform infrared spectroscopy (FT-IR). The results showed that DAAF/RDX microspheres exhibited regular shaped microspheres with sizes from 0.5 to 1.2 μm. There was no crystal transition during the modification process. The thermal properties of as-obtained materials were then evaluated by differential scanning calorimetry (DSC) and materials studio software. DAAF/RDX microspheres showed an advanced decomposition peak temperature compared with rod-like DAAF/RDX. The binding energy and peak temperature values at zero β_i (T_P0) of DAAF/RDX (90:10) increased by 36.77 kJ/mol, 1.6 °C, and 58.11 kJ/mol, 12.3 °C compared to DAAF/RDX (80:20) and DAAF/RDX (70:30), indicating the better thermal stability of DAAF/RDX (90:10). The characteristic drop height (H₅₀) of DAAF/RDX (higher than 100 cm) composites was higher than that of raw RDX (25 cm), suggesting significant improvements in mechanical safety. The preparation of DAAF/RDX microspheres is promising for the desensitization of RDX and useful for the formation of other materials and future wide applications.     

Formulation development and characterization of cellulose acetate nitrate based propellants for improved insensitive munitions properties

Cellulose acetate nitrate (CAN) was used as an insensitive energetic binder to improve the insensitive munitions (IM) properties of gun propellants to replace the M1 propellant used in 105 mm artillery charges. CAN contains the energetic nitro groups found in nitrocellulose (NC), but also acetyl functionalities, which lowered the polymer's sensitivity to heat and shock, and therefore improved its IM properties relative to NC. The formulation, development and small-scale characterization testing of several CAN-based propellants were done. The formulations, using insensitive energetic solid fillers and high-nitrogen modifiers in place of nitramine were completed. The small scale characterization testing, such as closed bomb testing, small scale sensitivity, thermal stability, and chemical compatibility were done. The mechanical response of the propellants under high-rate uni-axial compression at, hot, cold, and ambient temperatures were also completed. Critical diameter testing, hot fragment conductive ignition (HFCI) tests were done to evaluate the propellants' responses to thermal and shock stimuli. Utilizing the propellant chemical composition, theoretical predictions of erosivity were completed. All the small scale test results were utilized to down-select the promising CAN based formulations for large scale demonstration testing such as the ballistic performance and fragment impact testing in the 105 mm M67 artillery charge configurations. The test results completed in the small and large scale testing are discussed.     

Experimental investigation of a cook-off temperature in a hot barrel

The experimental investigations of the effect of contact time/temperature on initiating the cook-off using 7.62 mm calibre cartridge cases (CC) were conducted previously. These cartridges were filled with commercial off-the-shelf (COTS) double based (DB) propellant (Bulls Eye) and were loaded in a hot chamber. The thermal explosion temperature is of great significance to both weapon designers and safety inspectors as it provides the operational limit and safe operating temperature. For CC under test, it was found that the cook-off temperatures of this propellant were encountered with the heat transfer profile of the simulated gun barrel between 151.4 °C and 153.4 °C, with a reaction occurring in less than 300 s after the round was chambered. Usefully, each experiment was found to be consistent and repeatable.     

Thermal hazard assessment of TKX-50-based melt-cast explosive

In the present study, thermal hazards of TNT and DNAN used as the molten binder in TKX-50-based melt-cast explosives were comparatively studied through accelerating rate calorimeter (ARC) and Cook-off experiments. Two kinds of ARC operation modes were performed to investigate the thermal safety performance under adiabatic conditions (HWS mode) and constant heating (CHR mode). The obtained results demonstrated that at both heating modes, DNAN/TKX-50 outperformed TNT/TKX-50 from the thermal safety point of view. However, the sensitivity to heat of the samples was reverse because of the different heating modes. In addition, the results of thermal hazard assessment obtained from the cook-off experiment complied with ARC analysis which indicated the molten binder TNT replaced by DNAN would reduce the hazard of the TKX-50 melt cast explosive. Furthermore, the results of cook-off experiments also showed that DNAN/TKX-50 outperformed TNT/TKX-50 from the aspect of thermal stability, which was consistent with the result of CHR mode because of the similar heating process.     

A new experimental way for the monitoring of the real/equivalent in-service-time of double base rocket propellant by coupling VST and PCA

The assessment of the real in-service-time(RIST)and the equivalent in-service-time(EIST)of double base rocket propellants(DBRPs)is of utmost importance for the safe storage and use of weapon systems as well as the efficiency of the accelerated aging plans.In this work,four DBRPs with similar chemical composition and different natural aging have been artificially aged at T = 338.65 K for 4 months with sampling every 30 days.The unaged and artificially aged samples have been investigated by vacuum stability test(VST)at five isothermal temperatures(T = 333.15 K,343.15 K,353.15 K,363.15 K,and 373.15 K).The volume of the evolved gases in VST was found to decrease with natural/artificial aging.Furthermore,the VST data were treated and subjected to principal component analysis(PCA).The results showed excellent discrimination of the DBRP samples according to their stability thermal properties.Most of the variance was described by the first principal component(PC1)whose scores were linearly correlated with the natural aging durations when PCA is applied on VST data obtained at T = 363.15 K.In light of the obtained results,a new experimental way for the estimation of the real/equivalent IST was proposed,which takes into account the impact of the natural aging of the sample.The approach predicts successfully the RIST of two similar DBRPs with a relative deviation of less than 2％.At the specific heating temperature T = 338.65 K,the developed model provides more conceivable EIST values,with asymptotic behavior against artificial aging duration evolution,thus overcoming some shortcomings of the common generalized van't Hoff formula(GvH).     

Effect of organo-modified montmorillonite nanoclay on mechanical,thermal and ablation behavior of carbon fiber/phenolic resin composites

The mechanical, thermal and ablation properties of carbon phenolic (C-Ph) composites (Type-I) rein-forced with different weight percentages of organo-modified montmorillonite (o-MMT) nanoclay have been studied experimentally. Ball milling was used to disperse different weight (wt) percentages (0, 1,2,4,6 wt.％) of nanoclay into phenolic resin. Viscosity changes to resin due to nanoclay was studied. On the other hand, nanoclay added phenolic matrix composites (Type-II) were prepared to study the dispersion of nanoclay in phenolic matrix by small angle X-ray scattering and thermal stability changes to the matrix by thermogravimetric analyser (TGA). This data was used to understand the mechanical, thermal and ablation properties of Type-I composites. Inter laminar shear strength (ILSS), flexural strength and flexural modulus of Type I composites increased by about 29％, 12％and 7％respectively at 2 wt.％ addition of nanoclay beyond which these properties decreased. This was attributed to reduced fiber volume fraction (％Vf) of Type-I composites due to nanoclay addition at such high loadings. Mass ablation rate of Type-I composites was evaluated using oxy acetylene torch test at low heat flux (125 W/cm2) and high heat flux levels (500 W/cm2). Mass ablation rates have increased at both flux levels marginally up to 2 wt.％ addition of nanoclay beyond which it has increased significantly. This is in contrast to increased thermal stability observed for Type-I and Type-Ⅱ composites up to 2 wt.％addition of nanoclay. Increased ablation rates due to nanoclay addition was attributed to higher insulation effi-ciency of nanolcay, which accumulates more heat energy in limited area behind the ablation front and self-propagating ablation mechanisms triggered by thermal decomposition of organic part of nanoclay.     

Novel aluminum-based fuel: Facile preparation to improve thermal reactions

To improve the thermal properties of aluminum (Al) in the energetic system, a coated structure with ammonium perchlorate (AP) was prepared by a facile approach. And N, N-Dimethylformamide (DMF) was chosen as an ideal solvent based on heterogeneous nucleation theory and molecular dynamics simulation. This coated structure could enlarge the contact area and improve the reaction environment to enhance the thermal properties. The addition of AP could accelerate oxidation temperature of Al with around 17.5 °C. And the heat release of 85@15 composition rises to 26.13 kJ/g and the reaction degree is 97.6% with higher peak pressure (254.6 kPa) and rise rate (1.397 MPa/s). An ideal ratio with 15 wt% AP was probed primarily. The high energy laser-induced shockwave experiment was utilized to simulate the reaction behavior in hot field. And the larger activated mixture of coated powder could release more energy to promote the growth of shockwave with higher speed up to 518.7 ± 55.9 m/s. In conclusion, 85@15 composition is expected to be applied in energetic system as a novel metal fuel.     

Effect of energy content of the nitraminic plastic bonded explosives on their performance and sensitivity characteristics

Information about the forty nine nitraminic plastic bonded explosives (PBXs) and different nitramines were collected. Fillers of these PBXs are nitramines 1,3,5-trinitro-1,3,5-triazinane (RDX) and β-1,3,5,7-tetranitro-1,3,5-tetrazocane (β-HMX), cis-1,3,4,6-tetranitro-octahydroimidazo-[4,5-d]imidazole (bicyclo-HMX, BCHMX) and ε-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (ε-HNIW, CL-20) which are bonded by polyfluoro-elastomers, polydimethyl-siloxane, poly-glycidyl azide, polyisobutylene, polystyrene-butadiene, poly-acrylonitrile-butadiene and hydroxyl-terminated polybutadiene in addition to a melt cast compositions based on 2,4,6-trinitrotoluene. For thirty two of these PBXs the relationships are specified and analyzed between heats of their combustion and relative explosive strengths; by means of these relationships it might be possible to estimate, which groupings in the macromolecule of binder could be liable to their primary fission in the PBXs initiation. Similarly, for forty two of these explosives, the relationships are described and analyzed between their enthalpies of formation and impact sensitivities; here is especially attention paid to PBXs filled by BCHMX. Specific rate constants from Vacuum Stability Test (VST) of four nitramines and twenty PBXs are introduced into relationships with their enthalpies of formation. Regarding to all the mentioned cases, increasing of energy content of the studied explosives leads to increase of the relative explosive strength or initiation reactivity, respectively. Exception with the opposite trend, the outputs of VST are for BCHMX, where in PBXs are matrices with the esteric plasticizers or the energetic poly-glycidyl azide. Admixture of RDX or HMX, respectively, into the BCHX PBXs gives ternary PBXs whose thermal stability, in the sense of applied VST, is higher comparing to the original binary explosives.     

Thermal decomposition of ammonium perchlorate catalyzed with CuO nanoparticles

Ammonium perchlorate (APC) is the most common oxidizer in use for solid rocket propulsion systems. However its initial thermal decomposition is an endothermic process that requires 102.5 J·g⁻¹. This manner involves high activation energy and could render high burning rate regime. This study reports on the sustainable fabrication of CuO nanoparticles as a novel catalyzing agent for APC oxidizer. Colloidal CuO nanoparticles with consistent product quality were fabricated by using hydrothermal processing. TEM micrographs demonstrated mono-dispersed particles of 15 nm particle size. XRD diffractogram demonstrated highly crystalline material. The synthesized colloidal CuO particles were effectively coated with APC particles via co-precipitation by using fast-crash solvent–antisolvent technique. The impact of copper oxide particles on APC thermal behavior has been investigated using DSC and TGA techniques. APC demonstrated an initial endothermic decomposition stage at 242 °C with subsequent two exothermic decomposition stages at 297.8 °C and 452.8 °C respectively. At 1 wt%, copper oxide offered decrease in initial endothermic decomposition stage by 30%. The main outcome of this study is that the two main exothermic decomposition peaks were merged into one single peak with an increase in total heat release by 53%. These novel features can inherit copper oxide particles unique catalyzing ability for advanced highly energetic systems.     

The investigation of NTO/HMX-based plastic-bonded explosives and its safety performance

3-nitro-1,2,4-triazol-5-one (NTO) is the main component of insensitive munitions (IM) formulation because of its outstanding insensitive properties.In this paper,a series of NTO/HMX-based composite explosives were prepared and characterized.The study focuses on the effect of NTO on the performance of the formulations,especially the safety performance.The results revealed that the mechanical sensi-tivity of formulations was associated with NTO content,as well as the thermal conductivity,specific heat capacity and Arrhenius parameters.Then,the high amount of NTO using in formulation was proved to be helpful for NTO/HMX-based formulation to exhibit good thermal safety.Besides,by accelerating rate calorimeter (ARC) and a modified cook-offequipment,the pressure and pressure rise rate were proved as the important indicator for judging the thermal safety performance in confined spaces.Finally,the numerical simulation was used as a credible method for predicting the respond temperature of cook-off experiment.     

Nitro-tetrazole based high performing explosives: Recent overview of synthesis and energetic properties

Heterocyclic skeleton (Azoles) and different energetic groups containing high performing explosives are highly emerged in recent years to meet the challenging requirements of energetic materials in both military and civilian applications with improved performance. For this purpose tetrazole (Azole) is identified as an attractive heterocyclic backbone with energetic functional groups nitro (-NO₂), nitrato (-ONO₂), nitrimino (-NNO₂), and nitramino (–NH–NO₂) to replace the traditionally used high performing explosives. The tetrazole based compounds having these energetic functional groups demonstrated advanced energetic performance (detonation velocity and pressure), densities, and heat of formation (HOF) and became a potential replacement of traditional energetic compounds such as RDX. This review presents a summary of the recently reported nitro-tetrazole energetic compounds containing poly-nitro, di/mono-nitro, nitrato/nitramino/nitrimino, bridged/bis/di tetrazole and nitro functional groups, describing their preparation methods, advance energetic properties, and further applications as high-performing explosives, especially those reported in the last decade. This review aims to provide a fresh concept for designing nitro-tetrazole based high performing explosives together with major challenges and perspectives.     

金属热防护系统瞬态热分析的并联一维模型

建立了可重复使用运载器金属热防护系统瞬态热分析的并联一维模型.根据热防护系统的结构特点划分了多条热流通路,将各热流通路离散化后给出了单条通路瞬态传热的隐式差分格式,采用热平衡法推导了串、并联两种类型公共节点的局部控制方程,并给出了传热问题中常见边界条件的统一表达式,最终形成了总体控制方程.通过数值计算获得了热防护系统瞬态温度场.计算结果表明:采用并联一维模型可以更真实、更准确地反映热防护系统的传热过程,对于热防护系统结构优化设计有较高的参考价值.     

基于可行使用方案的舰船热力系统RMS仿真论证研究

舰船热力系统因使用、故障、维修和保障的复杂性,通过建立数学模型的解析方法不能满足其RMS论证的需要,而基于最小设备清单的MonteCarlo仿真法也因组成设备存在性能退化而不适合作为系统的故障判据。文章利用基于热力模型确定的可行使用方案替代基于逻辑关系确定的最小设备清单,按照系统在部分设备故障后是否还具有可行使用方案来判别系统是否故障,设计了基于可行使用方案的舰船热力系统RMS仿真流程,在仿真流程改进的基础上编制了舰船热力系统RMS论证软件。算例验证表明,改进的流程能够在保证仿真精度的同时,具有较高的计算效率。     

Cross-linking density and aging constitutive model of HTPB coating under prestrain thermal accelerated aging

In order to study the cross-linking density and aging constitutive relationship of HTPB coating during storage, the thermal accelerated aging tests at 0%, 3%, 6% and 9% prestrains were carried out. The cross-linking density of HTPB coating at different aging stages were tested using low-field ¹H NMR and the variation of cross-linking density was analyzed. The aging model of cross-linking density considering the chemical aging and the physical stretching factors was established. The uniaxial tensile tests were carried out on HTPB coating at different aging stages and the cross-linking density was introduced into Ogden hyperelastic constitutive model as a characterization parameter of correction coefficient. Combined with uniaxial tensile test results, a prestrain aging constitutive model of HTPB coating was established. The results show that the cross-linking density of HTPB coating increases rapidly at first and then slowly with the increase of thermal accelerated aging time without prestrain. Under prestrain conditions, the cross-linking density of HTPB coating decreases at the early stage, and increases rapidly at first and then slowly at the middle and late stages of thermal accelerated aging. The correlation coefficients of aging model of cross-linking density and aging constitutive model with test results are R > 0.9500 and R > 0.9900 respectively, which can be used to accurately describe the cross-linking density and aging constitutive relationship of HTPB coating under prestrain accelerated thermal aging conditions.     

功率循环下IGBT模块电热参数变化规律分析

为了分析IGBT模块老化过程中电热参数的变化规律,对IGBT模块进行了功率循环加速老化试验,并基于单脉冲测试方法在加速老化试验进程中每间隔1 000次功率循环,测取一次IGBT的结温、集电极电流与饱和压降三维关系曲面、开关能耗、热阻抗以及瞬态热阻抗曲线。IGBT模块老化失效时,其饱和压降、开通能耗、关断能耗以及热阻较其初始值分别增大了3.92%、12.05%、18.87%和22.65%,试验结果表明随着IGBT模块功率循环次数的增多,相同工作条件下IGBT饱和压降的增幅逐渐加大,而饱和压降、结温和集电极电流三者间的内在关系没有明显变化;IGBT瞬态热阻抗曲线暂态部分几乎不变,稳态部分向上移动的幅度逐渐加大;测取的IGBT模块电热参数中饱和压降增幅最小,开关能耗增幅较大,模块热阻的增幅最为明显。     

Enhancing the explosive characteristics of a Semtex explosive by involving admixtures of BCHMX and HMX

A well-known ternary plastic explosive, Czech Semtex 1H, contains a mixture of PETN and RDX softened by SBR. In this work, BCHMX was used to replace PETN in Semtex 1H to form Sem-BC+RDX. In addition, another mixture based on BCHMX and HMX as energetic fillers bonded by the polymeric matrix of Semtex 1H (Sem-BC+HMX) was studied. The particle size distribution of each individual explosive was determined to obtain the optimum mixing conditions. Friction and impact sensitivities were determined. The velocity of detonation was reported practically and the detonation properties were calculated by EXPLO5 code. The explosive strength of each sample was measured by the ballistic mortar test. The conclusion confirms that the velocity of detonation of Sem-BC+HMX was the highest in comparison with the prepared samples. Sem-BC+RDX has the least impact and frictions sensitivities. Sem-BC+RDX has higher detonation velocity, detonation properties and explosive strength than Semtex 1H. Addition of BCHMX in Semtex 1H as a replacement for PETN is the candidate to produce a high performance advanced Czech plastic explosive.     

高超声速滑翔飞行器气动性能的数值模拟研究

由于具有高的升阻比,乘波构型被认为是高超声速滑翔飞行器的重点参考外形.考虑到高超声速条件下严重的气动加热问题,乘波构型的尖锐前缘需要进行钝化处理,其表面流动特征及气动性能也随之发生变化.基于参考弹道,本文分析了高超声速滑翔飞行器沿飞行轨迹的表面流场特征,并对其在典型飞行工况下的气动性能开展了数值模拟研究.结果表明:对于采用乘波布局设计的高超声速滑翔飞行器,其驻点流动存在三维效应,不能简单视为球头或圆柱绕流;钝化可以缓和严峻的受热形势,同时对其气动力性能造成影响:在2cm钝化半径条件下,其升阻比下降12.34％;高超声速滑翔飞行器的表面受热存在明显的分区特征,不同区域可采用不同的防热处理方法.     

传导冷却高温超导磁体热输运参数反演识别

在传导冷却高温超导磁体系统中,超导磁饼热导率以及磁饼与导冷体之间的界面热阻是影响热输运的主要因素,也是传导冷却超导磁体系统热设计的难点。为了获得准确的热导率和界面热阻参数,根据Levenberg-Marquardt算法提出通过表面测温确定传导冷却超导磁体热输运参数的反演识别方法。搭建低温实验数据测试平台,建立高温超导磁饼三维各向异性热传导模型。利用反演算法对传导冷却Bi2223高温超导磁体在40~76K温区的各向异性热导率与界面热阻进行反演识别,并分析测温误差对识别结果的影响。研究成果将为超导磁体热输运参数的获取提供一种新思路。     

舰船电缆热老化寿命的研究

介绍了某船用电缆热老化寿命研究的有关试验和结果分析．对电统绝缘材料失效的判断、机械性能变化的预测,以及如何根据电缆的负载情况和周围的环境温度确定绝缘材料的老化温度等,提出了相应的观点和方法．     

发动机排气门座温度场与应力场有限元分析

根据弹塑性理论和传热学原理建立了坦克发动机排气门座在发动机加载条件下温度场和应力场的计算模型,并采用非线性有限元分析法研究了其热应力和机械应力的分布状态及其变化规律,为排气门座优选材料和结构优化提供了理论依据.