Nanothermite colloids: A new prospective for enhanced performance

Nanothermites (metal oxide/metal) can offer tremendously exothermic self sustained reactions. CuO is one of the most effective oxidizers for naonothermite applications. This study reports on two prospectives for the manufacture of CuO nanoparticles. Colloidal CuO particles of 15 nm particle size were developed using hydrothermal synthesis technique. Multiwalled carbon nanotubes (MWCNTs) with surface are 700 m²/g was employed as a substrate for synthesis of CuO-coated MWCNTs using electroless plating. On the other hand, aluminium particles with combustion heat of 32000 J/g is of interest as high energy density material. The impact of stoichiometric nanothermite particles (CuO/Al & Cuo-coated MWCNTs/Al) on shock wave strength of Al/TNT nanocomposite was evaluated using ballistic mortar test. While CuO-coated MWCNTs decreased the shock wave strength by 15%; colloidal CuO enhanced the shock wave strength by 30%. The superior performance of colloidal CuO particles was correlated to their steric stabilization with employed organic solvent. This is the first time ever to report on fabrication, isolation, and integration of stablilized colloidal nanothermite particles into energetic matrix where intimate mixing between oxidizer and metal fuel could be achieved.     

The non-isothermal gravimetric method for study the thermal decomposition kinetic of HNBB and HNS explosives

The hexanitrostilben (HNS) is a thermally stable explosive that can be prepared from hexanitrobibenzyl (HNBB). Therefore, the investigation of thermal stability of HNBB can be important in the yield of preparation of HNS. The decomposition kinetic of HNBB and HNS are studied by non-isothermal gravimetric method. The TG/DTG curves in non-isothermal method are obtained in range of 25°C–400 °C at heating rates of 3 °C/min, 5 °C/min, 8 °C/min, 10 °C/min and 12 °C/min. The data of weight-temperature are used for calculation of activation energy (E_a) of thermal decomposition reactions by methods of Ozawa, Kissinger, Ozawa-Flynn-Wall (OFW) and Kissinger-Akahira-Sunose (KAS) as model-free methods and Strink's equation as model-fitting method. The compensation effect is used for prediction of mechanism and determination of pre-exponential factor (lnA) of the decomposition reaction. A reduction 60 kj/mol for the average of activation energy of thermal decomposition reaction of HNBB is obtained versus HNS. This result shows the lower thermal stability of HNBB in comparison to HNS. The Avrami equation (A_3/2) with function f(α) = 3/2(1-α)[-ln(1-α)]^1/3 indicates the predicted mechanism for thermal decomposition reaction both explosives.     

Scale-up synthesis and characterization of 2,6-diamino-3,5-dinitropyrazine-1-oxide

2,6-diamino-3,5-dinitropyrazine-1-oxide (ANPZO), as an insensitive high explosive, with a high yield and excellent purity has been prepared at pilot plant scale by an improved method. The synthesized ANPZO is characterized by IR, laser granularity measurement, SEM and HPLC. The particle analysis revealed that the improved method could offer desired product with average particle size of 40 μm and high purity (>98.45%). The experimental parameters exhibited that the detonation velocity of the formulation based on ANPZO was higher than that of the corresponding TATB formulation. The DSC curve showed that the exothermic decomposition of the product occurred at the temperature between 300.5 °C and 360.4 °C. Furthermore, the sensitivity test suggests its safe nature towards mechanical stimulus.     

Liquid phase in-situ synthesis of LiF coated boron powder composite and performance study

Among practical metal additives, boron (B) has a high volumetric heating value, making it a promising choice as a fuel additive. Although B can theoretically yield a large amount of energy upon complete combustion, its combustion is retarded by the initial presence of B oxide, which coats the surfaces of B particle. To improve the ignition and combustion properties of B powder, LiOH and NH₄F were used as precursors to synthesize uniformly LiF-coated B composites (LiF-B) in situ. The LiF-B mixture was also prepared for comparison using a physical method. X-ray diffraction (XRD), Fourier-transform infrared (FTIR), scanning electron microscope (SEM), and energy-dispersive X-ray spectroscopy (EDS) were used to characterize the morphologies and compositions of the products. The thermal and combustion properties of the samples were characterized by thermal gravity-differential thermal gravity (TG-DTG), differential scanning calorimetry (DSC) and closed bomb experiment. The XRD, FTIR, SEM and EDS results demonstrated the successful preparation of the coated LiF-B sample. The TG-DTG and closed bomb experiment results indicated that the addition of LiF decreased the ignition temperature of B powder, and increasing its reaction efficiency. DSC results show that when LiF-B was added, the released heat of underwater explosive increased by 6727.2, 7280.4 and 3109.6 J/g at heating rates of 5, 10, and 15 °C/min, respectively. Moreover, LiF-B decreased the activation energy of secondary combustion reaction of explosive system as calculated through Kissinger's method by 28.9%, which indicated an excellent catalytic effect for the thermal decomposition of underwater explosive. The results reveal that LiF can improve the combustion efficiency of B powder, thereby increasing the total energy of explosives. The mechanical sensitivity increased slightly after adding LiF-B to the underwater explosive. Compared to the underwater explosive with added B, the mechanical sensitivity of the explosive with added LiF-B was significantly lower.     

Effect of microstructure on short pulse duration shock initiation of TATB and initial response mechanism

Micro-TATB particles with different sizes and 3D nanoporous TATB architectures with different specific surface areas were prepared through recrystallization to study short pulse duration shock initiation properties by electric gun technology. For micro-TATB, the initiation threshold significantly decreases with TATB average size ranging from 79.7 μm to 0.5 μm. For 3D nanoporous TATB architecture, the initiation threshold decreases and then increases with specific surface areas increased from 9.6 m²/g to 36.2 m²/g. The lowest initiation thresholds are obtained for the micro-TATB with average sizes of 1.3 μm and 0.5 μm, and 3D nanoporous TATB architecture with specific surface area of 22.4 m²/g. The shock initiation thresholds of micro-TATB and 3D nanoporous TATB architectures show significantly decreases with the porosity increased. The decomposition reaction and thermal conductivity properties were further investigated to understand the initial response mechanism. High porosity provides more collapse sites to generate high temperature for formation of hot spots. The low thermal conductivity and decomposition temperature could enhance the formation and ignition of the hot spots, and initial decomposition reaction of TATB. The effect of the decomposition temperature is higher than that of the thermal conductivity on the shock initiation properties. The enhanced decomposition reaction could promote energy release and transfer process from the ignition to the combustion. This work offers a new insight to understand the effects of microstructure on the shock initiation properties and the initial response mechanism of TATB.     

Design of infrared camouflage cloak for underground silos

The temperature difference between the exposed surface of an underground silo and the surrounding soil surface is significant, which means a silo can be easily found by infrared detection. We designed an infrared camouflage cloak consisting of an imitative layer and an insulation layer for the silos. The imitative layer is used to imitate the thermal response of the soil to the surrounding environment. The insulation layer is used to weaken the impact of the internal temperature field of the silo on the lower boundary of the imitative layer. A silo model including surrounding soil and a soil model without silo were established, and the influences of the material and thickness of each layer on the infrared camouflage effect were analyzed. The results show that when using a silicone rubber containing alumina powder with a volume fraction of 3.18% as the imitative material, its thermal inertia is in consistent with that of the soil. Meanwhile, it was found that the thickness of the imitative layer doesn’t need to be greater than its thermal penetration depth to achieve the infrared camouflage, and the absence of the insulation layer will cause hot spots on the silo surface in winter to weaken the camouflage effect. The optimized thicknesses of the imitative layer and the insulation layer are 22 cm and 4 cm respectively. The simulations indicate that with the application of the cloak, the maximum value of the absolute values of the temperature differences between the average temperatures of the silo surface and the surrounding soil surface temperatures drops from 1.59 °C to 0.31 °C in summer and from 1.92 °C to 0.21 °C in winter. This designed cloak can achieve an all-weather and full-time passive infrared camouflage.     

Effect of nano powder (Al2O3-CaO) addition on the mechanical properties of the polymer blend matrix composite

This work describes the preparation and study of the properties of composite nanoparticles prepared by the sol-gel method which consists of two materials (Al₂O₃-CaO), and study the effect of these nanoparticles on the mechanical behavior of a polymer blend (EP 4% + 96% UPE). The powder was evaluated by X-ray diffraction analysis, scanning electron microscopy analysis (SEM), particle size analysis, and energy dispersive X-ray analysis (EDX). The mechanical behavior of the composite material was assessed by tensile test, bending test and hardness test. The evaluation results of the composite nanoparticles showed good distribution of the chemical composition between aluminum oxide and calcium oxide, smoothness in particles' size at calcination in high and low temperatures, formation of different shapes of nanoparticles and different (kappa and gamma) phases of the Al₂O₃ particles. The results of mechanical behavior tests showed marked improvement in the mechanical properties of the resulted composite material, especially at 1.5%, compared with polymer blend material without nano powder addition. The tensile properties improved about (24 and 14.9) % and bending resistance about (23.5 and 16.8) % and hardness by (25 and 22) % when adding particles of size (63.8 and 68.6) respectively. Therefore, this reflects the efficiency of the proposed method to manufacture the nanocomposite powder and the possibility of using this powder as a strengthening material for the composite materials and using these composite materials in bio applications, especially in the fabrication of artificial limbs.     

先驱体转化致密SiC纳米复合材料的制备及其热电性能

以聚碳硅烷和锑改性聚硅烷为先驱体,利用先驱体转化SiC材料的富余自由碳高温石墨化的微观结构演变特点,采用热压烧结、先驱体浸渍—裂解法以及退火工艺制备出先驱体转化SiC纳米复合材料。采用SEM、TEM、XRD和Raman等测试手段表征和分析了相组成和微观结构,讨论了样品的热导率、电导率和塞贝克系数等热电参数随温度变化关系。研究表明,所得致密SiC纳米复合材料为n型热电材料。由于纳米石墨的作用,材料热导率抑制在4–8W/(m?K)范围。1600°C退火处理能够降低热导率,同时提高电导率和塞贝克系数绝对值,使先驱体转化法得到的SiC纳米复合材料无量纲热电优值ZT达到0.0028（650°C）,高于其他已报道的致密SiC/C复合材料和纳米复合材料体系。     

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.     

聚溴化苯乙烯阻燃聚乙烯热解动力学研究

用聚溴化苯乙烯作为阻燃剂，制备了阻燃聚乙烯（PE），利用TG方法研究了PE和阻燃PE在氮气气氛下的热解动力学行为，并用改进的非等温动力学方法研究了其热解动力学。结果表明，加入阻燃剂后材料的初始分解温度提前，阻燃材料的热解区间变宽，阻燃体系的平均失重速率下降，最大失重速率下降，主要分解阶段的残炭率高于未阻燃PE，聚溴化苯乙烯阻燃效果明显，可用于聚乙烯阻燃，说明大分子溴系阻燃剂具有较好的发展潜力。氮气气氛下未阻燃聚乙烯的热解过程只存在一个失重阶段，而阻燃材料在相同温度范围内呈现不同的失重阶段，且在各失重阶段其反应机理函数也发生变化；活化能、指前因子都有所不同，阻燃材料的活化能大于未阻燃材料，且活化能在整个失重阶段是随着温度和转化率的变化而变化的，说明阻燃剂的加入改变了材料的热解行为。     

Vapor-phase decomposition of dimethyl methylphosphonate (DMMP), a sarin surrogate,in presence of metal oxides

Chemical warfare agents (CWA) are stockpiled in large quantities across the globe. Agents stored in inaccessible facilities need to be destroyed rapidly without dispersing the compounds to surrounding areas. Metal-based energetic formulations are used in such prompt defeat applications to rapidly decompose the CWA by generating a high temperature environment. An alternate, and possibly a more effective decomposition pathway could be provided by chemicidal action of aerosolized condensed combustion products, which typically consist of metal oxides. Toxic fumes that escape the high tem-perature blast zone can be neutralized by smoke generated during combustion, depending on the par-ticle size, surface characteristics, chemical properties, and concentration of this smoke. This review considers relevant experimental and modeling studies quantifying decomposition of CWA comprising organophosphorus compounds and their surrogates on the surface of various metal oxides. Dimethyl methylphosphonate (DMMP), a sarine surrogate, was used most commonly for such experiments. Many reported efforts focused on the mechanisms of adsorption of DMMP to various metal oxides and initial reaction steps cleaving various bonds from the chemisorbed molecules. For selected oxides, these ex-periments were supported by quantum-mechanical calculations. In other studies, the capacity of oxide surfaces to adsorb and decompose DMMP was quantified. In most cases, porous catalysts were used although limited experimental data are available for aerosolized nonporous oxide particles. The reported experimental data applicable to scenarios involving prompt decomposition of CWA are summarized. It is noted that information is lacking describing respective heterogeneous reaction kinetics. Preliminary estimates of aerosolized smoke particle concentrations required to destroy CWA are made considering gas phase diffusion rates and reported values of the oxide capacity to decompose CWA or their surrogates.     

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.     

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.     

Tuning the reactivity of Al–Ni by fine coating of halogen-containing energetic composites

In this paper, various core-shell structured Al–Ni@ECs composites have been prepared by a spray-drying technique. The involved ECs refer to the energetic composites (ECs) of ammonium perchlorate/nitrocellulose (AP/NC, NA) and polyvinylidene fluoride/hexanitrohexaazaisowurtzitane (PVDF/CL-20, PC). Two Al–Ni mixtures were prepared at atomic ratios of 1:1 and 1:3 and named as Al/Ni and Al/3Ni, respectively. The thermal reactivity and combustion behaviors of Al–Ni@ECs composites have been comprehensively investigated. Results showed that the reactivity and combustion performance of Al–Ni could be enhanced by introducing both NA and PC energetic composites. Among which the Al/Ni@NA composite exhibited higher reactivity and improved combustion performance. The measured flame propagation rate (v = 20.6 mm/s), average combustion wave temperature (T_max = 1567.0 °C) and maximum temperature rise rate (γ_t = 1633.6 °C/s) of Al/Ni@NA are higher than that of the Al/Ni (v = 15.8 mm/s, T_max = 858.0 °C, and γ_t = 143.5 °C/s). The enhancement in combustion properties could be due to presence of the acidic gaseous products from ECs, which could etch the Al₂O₃ shell on the surface of Al particles, and make the inner active Al to be easier transported, so that an intimate and faster intermetallic reaction between Al and Ni would be realized. Furthermore, the morphologies and chemical compositions of the condensed combustion products (CCPs) of Al–Ni@ECs composites were found to be different depending on the types of ECs. The compositions of CCPs are dominated with the Al–Ni intermetallics, combining with a trace amount of Al₅O₆N and Al₂O₃.     

SPH并行计算方案及其在自由表面流动模拟中的应用

针对光滑粒子动力学主要计算量是近邻粒子搜索这一特点,提出了一种基于粒子分解的光滑粒子动力学并行计算方案。利用该方案可以方便地将任意串行光滑粒子动力学代码并行计算,而且每一个时间步内的信息传递量只和粒子总数有关,而和粒子的分布无关,因而特别适合于自由表面流动等大变形问题的并行数值模拟。对一个粒子总数为40万的三维溃坝问题的模拟结果表明:此方案能达到的最大加速比约为16,这一结果可能比空间分解方案(不考虑动态负载均衡)更优。     

Ni-Zn铁氧体粉末的溶胶-凝胶合成及微波性能

以硝酸铁、硝酸镍、硝酸锌、柠檬酸和氨水为原料,用溶胶-凝胶法合成了不同组成的Ni-Zn铁氧体粉末。利用热分析、X射线衍射等手段研究了干凝胶热分解行为。利用网络分析仪对铁氧体粉末的电磁性能进行了表征,考察了铁氧体的组成与其电磁性能之间的关系。结果表明,溶胶-凝胶法合成的铁氧体粉末的μ″值随测试频率的提高和Ni-Zn铁氧体中锌含量的增加而减小。     

DEA models for two‐stage processes: Game approach and efficiency decomposition

Data envelopment analysis (DEA) is a method for measuring the efficiency of peer decision making units (DMUs). This tool has been utilized by a number of authors to examine two‐stage processes, where all the outputs from the first stage are the only inputs to the second stage. The current article examines and extends these models using game theory concepts. The resulting models are linear, and imply an efficiency decomposition where the overall efficiency of the two‐stage process is a product of the efficiencies of the two individual stages. When there is only one intermediate measure connecting the two stages, both the noncooperative and centralized models yield the same results as applying the standard DEA model to the two stages separately. As a result, the efficiency decomposition is unique. While the noncooperative approach yields a unique efficiency decomposition under multiple intermediate measures, the centralized approach is likely to yield multiple decompositions. Models are developed to test whether the efficiency decomposition arising from the centralized approach is unique. The relations among the noncooperative, centralized, and standard DEA approaches are investigated. Two real world data sets and a randomly generated data set are used to demonstrate the models and verify our findings. © 2008 Wiley Periodicals, Inc. Naval Research Logistics, 2008     

Modeling multiple stage manufacturing systems with generalized costs and capacity issues

This study introduces one modeling methodology that describes a broad range of multiple stage production planning issues, including multiple limited resources with setup times and joint fixed cost relationships. An existing production system is modeled in this fashion, creating a new set of 1350 highly generalized benchmark problems. A computational study is conducted with the 1350 benchmark problems introduced in this paper and 2100 benchmark problems, with more restrictive assumptions, from the existing literature. The relative merits of a decomposition‐based algorithm and a neighborhood search technique known as NIPPA, or the Non‐sequential Incremental Part Period Algorithm, are assessed. NIPPA is generally the more successful of the two techniques, although there are specific instances in which the decomposition‐based algorithm displayed a distinct advantage. © 2005 Wiley Periodicals, Inc. Naval Research Logistics, 2005     

An integer decomposition algorithm for solving a two‐stage facility location problem with second‐stage activation costs

We study a stochastic scenario‐based facility location problem arising in situations when facilities must first be located, then activated in a particular scenario before they can be used to satisfy scenario demands. Unlike typical facility location problems, fixed charges arise in the initial location of the facilities, and then in the activation of located facilities. The first‐stage variables in our problem are the traditional binary facility‐location variables, whereas the second‐stage variables involve a mix of binary facility‐activation variables and continuous flow variables. Benders decomposition is not applicable for these problems due to the presence of the second‐stage integer activation variables. Instead, we derive cutting planes tailored to the problem under investigation from recourse solution data. These cutting planes are derived by solving a series of specialized shortest path problems based on a modified residual graph from the recourse solution, and are tighter than the general cuts established by Laporte and Louveaux for two‐stage binary programming problems. We demonstrate the computational efficacy of our approach on a variety of randomly generated test problems. © 2010 Wiley Periodicals, Inc. Naval Research Logistics, 2010