Fullerene bisadduct stabilizers: The effect of different addition positions on inhibiting the autocatalytic decomposition of nitrocellulose absorbed nitroglycerin

To explore the effect of different positions and number of pyrrolidine bound to the carbon cage on the stabilization effect of fulleropyrrolidine derivatives to nitrocellulose (NC)/nitroglycerine (NG), we synthesized N-(4-methoxy) phenylpyrrolidine-C₆₀ and four different of bis(N-(4-methoxy) phenylpyrrolidine)-C₆₀ compounds through Prato reaction. Their structures were characterized by UV–vis, ¹H NMR, ¹³C NMR, high-resolution mass spectroscopy, and single-crystal X-ray diffraction. Their stabilization effect to NC/NG were investigated using differential scanning calorimetry, methyl violet, vacuum stabilization effect, weight loss, and accelerating rate calorimeter tests. The results indicated these compounds had excellent stabilization effect to NC/NG. The stabilization effect of the fulleropyrrolidine bisadducts to NC/NG is significantly better than that of fulleropyrrolidine monoadduct and C₆₀. Moreover, the position where pyrrolidine binds to fullerene in fulleropyrrolidine bisadducts is different, and its stabilization effect to NC is also different. The stabilization effect order of different bisadduct isomers to nitrocellulose is as follows: e-edge > trans-2> cis-2> trans-3. Electron paramagnetic resonance (EPR) and FT-IR were used to study the stabilization mechanism of fulleropyrrolidine derivatives to NC/NG. The EPR results also show that fulleropyrrolidine bisadducts with different addition sites have different abilities to absorb nitroxide, and their ability is better than that of the monoadduct and C₆₀, which is consistent with the results of stabilization effect performance test.     

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。     

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.     

The surface activation of boron to improve ignition and combustion characteristic

Boron is a very promising and highly attractive fuel because of high calorific value. However, the practical applications in explosives and propellants of boron have been limited by long ignition delay time and low combustion efficiency. Herein, nano-Al and graphene fluoride (GF) as surface activated materials are employed to coat boron (B) particles to improve ignition and combustion performance. The reaction heat of nano-Al coated B/KNO₃ and GF coated B/KNO₃ are 1116.83 J/g and 862.69 J/g, respectively, which are higher than that of pure B/KNO₃ (823.39 J/g). The ignition delay time of B/KNO₃ could be reduced through nano-Al coating. The shortest ignition delay time is only 75 ms for B coated with nano-Al of 8 wt%, which is much shorter than that of pure B/KNO₃ (109 ms). However, the ignition delay time of B/KNO₃ coated with GF has been increased from 109 to 187 ms. B coated with GF and nano-Al shown significantly influence on the pressure output and flame structure of B/KNO₃. Furthermore, the effects of B/O ratios on the pressure output and ignition delay time have been further fully studied. For B/KNO₃ coated with nano-Al and GF, the highest pressures are 88 KPa and 59 KPa for B/O ratio of 4:6, and the minimum ignition delay time are 94 ms and 148 ms for B/O ratio of 7:3. Based on the above results, the reaction process of boron coated with GF and nano-Al has been proposed to understand combustion mechanism.     

A study of flames with millimeter-wave radiation

It is a valuable issue to explore whether a flame can radiate microwaves, in spite of the electric field formed in the flame. Presented herein is an experimental study on a series of flames with millimeter-wave radiation in the combustion of pyrotechnic films. The pyrotechnic films were composed of ultra-fine red phosphorus (P), sodium nitrate (NaNO₃), Polyvinyl Alcohol (PVA) and some additives such as chopped carbon fibers (CFs) and aluminized glass fibers (GFs). The combustion temperatures and millimeter-wave radiation signals of the flames were measured, the millimeter-wave emissivity and spectral radiant exitance were calculated to describe the millimeter-wave radiation intensity. The results demonstrate that the flame of the pyrotechnic films based on P/NaNO₃/CFs can radiate millimeter waves, and different materials and their proportion have a great effect on the millimeter-wave radiation intensity.     

二维 DFT 和 DCT 的 Systolic 阵列

超级计算中一个活跃的研究领域是将某些有限和,如离散富里叶变换(DFT)、离散余弦变换(DCT),映射到多处理机阵列上。本文首先通过二维DFT的行列分解算法流程图,给出了计算二维DFT的二种Systolic阵列:一种是由N_1个处理器组成的线性阵列,所花时间步为O(N_1N_2)(设二维DFT为N_1×N_2长的),与行列分解算法在单处理机上顺序执行所花时间相比,加速比为O(N)(设N_1=N_2=N)。这一结果无论是在时间消耗,还是在PE数量上都是目前最优的。另一种是由N_1×N_2个处理器组成的矩形阵列,所需时间为O(N_1+N_2),与行列算法在单处理机上顺序运行所花时间相比,加速比为O(N~2)(这里仍假定N_1=N_2=N)。本文还给出了二维DCT的与二维DFT相似的Systoilc阵列结构。不难将上述阵列推广到多维的情况。     

Combustion of B4C/KNO3 binary pyrotechnic system

Presented herein is an experimental study on the combustion of B4C/KNO3 binary pyrotechnic system.Combustion products were tested using X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive spectrometer(EDS).According to the results of tests and CEA calculation,the combustion reaction equation was established.The flames and burning rates were recorded by a high speed camera and a spectrophotometer.The effect of B4C particle size on the thermal sensitivity of B4C/KNO3 was investigated by differential scanning calorimetry(DSC)techniques.In addition,a reliable method for calculating the flame temperature was proposed.Based on the results of experiments,the combustion reaction mechanism was briefly analyzed.The burning rate,flame temperature and thermal sensitivity of B4C/KNC3 increase with the decrease of B4C particle size.The mass ratio of B4C/KNO3 has a great effect on combustion properties.Oxidizer-rich compositions have low flame temperatures,low burning rates,and provide green light emission.The combustion reactions of fuel-rich compositions are vigorous,and the B4C/KNO3 with mass ratio of 25:75 has the highest burning rate and the highest flame temperature.     

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.     

Preparation and characterization of HMX/NH2-GO composite with enhanced thermal safety and desensitization

To improve the safety of HMX, HMX/NH₂-GO composite was prepared with aqueous ammonia functionalized graphene oxide (NH₂-GO). The composite was characterized by SEM, Zeta potential, XPS, Raman spectrum, XRD, HPLC, DSC and BAM sensitivity test. The results indicated that the functionalization with aqueous ammonia can enhance the interaction between GO and HMX, and more efficiently desensitize the explosive. The optimal impact sensitivity of the HMX/NH₂-GO composite can be not less than 40 J, which is also the most insensitivity compared to the previous reports prepared by coating desensitization with non-energetic desensitized material. Moreover, the potential reason for the different impact and friction sensitivity was also discussed, which may bring a novel perspective to achieve the desensitization of energetic material.     

Readiness and the optimal redeployment of resources

This paper considers the problem of the optimal redeployment of a resource among different geographical locations. Initially, it is assumed that at each location i, i = 1,…, n, the level of availability of the resource is given by a₁ ≧ 0. At time t > 0, requirements R_f(t) ≧ 0 are imposed on each location which, in general, will differ from the a₁. The resource can be transported from any one location to any other in magnitudes which will depend on t and the distance between these locations. It is assumed that ΣR_j > Σa_t The objective function consideis, in addition to transportation costs incurred by reallocation, the degree to which the resource availabilities after redeployment differ from the requirements. We shall associate the unavailabilities at the locations with the unreadiness of the system and discuss the optimal redeployment in terms of the minimization of the following functional forms: \documentclass{article}\pagestyle{empty}\begin{document}$ \sum\limits_{j = 1}^n {kj(Rj - yj) + } $\end{document} transportation costs, Max \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {Max}\limits_j \,[kj(Rj - yj)] + $\end{document} transportation costs, and \documentclass{article}\pagestyle{empty}\begin{document}$ \sum\limits_{j = 1}^n {kj(Rj - yj)^2 + } $\end{document} transportation costs. The variables y_j represent the final amount of the resource available at location j. No benefits are assumed to accrue at any location if y_j > R_j. A numerical three location example is given and solved for the linear objective.     

Optimizing the defensive characteristics of mild steel via the electrodeposition of ZnSi3N4 reinforcing particles

The effect of ZnSi₃N₄ deposition prepared via direct electrolytic co-deposition on mild steel was studied as a result its inherent vulnerability to corrosion in an aggressive environment and failure on the application of load. The experiment was conducted varying the mass concentration of silicon nitride (Si₃N₄) between 7 and 13 g at cell voltage of 0.3 and 0.5 V, at constant temperature of 45 °C. The morphologies of the coated surfaces were characterized using high resolution Nikon Optical Microscope and Scanning Electron Microscope (SEM) revealing that the particles of the ZnSi₃N₄ were homogeneously dispersed. The corrosion behaviour was studied using potentiodynamic polarization technique in 3.65% NaCl solution and the microhardness was examined using Brinell hardness testing technique. The result of the corrosion experiment confirmed an improved corrosion resistance with a reduction in corrosion rate from 9.7425 mm/year to 0.10847 mm/year, maximum coating efficiency of 98.9%, maximum polarization resistance of 1555.3 Ω and a very low current density of 9.33 × 10⁻⁶ A/cm². The negative shift in the E_corr revealed the cathodic protective nature of the coating. The microhardness was also found to have increased from 137.9 HBN for the unmodified steel to a maximum value of 263.3 HBN for the 0.5Zn13Si₃N₄ coated steel representing 90.9% increment in hardness as a result of the matrix grain refining and dispersion-strengthening ability of the incorporated Si₃N₄ particles.     

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.     

Estimation of the kinetic parameters for thermal decomposition of HNIW and its adiabatic time-to-explosion by Kooij formula

A differential/integral method to estimate the kinetic parameters (apparent activation energy E_a and pre-exponential factor A) for thermal decomposition reaction of energetic materials based on Kooij formula are applied to study the nonisothermal decomposition reaction kinetics of hexanitrohexaazaisowurtzitane (HNIW) by analyzing nonisothermal DSC curve data. The apparent activation energy (E_a) obtained by the integral isoconversional non-isothermal method based on Kooij formula is used to check the constancy and validity of apparent activation energy by the differential/integral method based on Kooij formula. The most probable mechanism function of thermal decomposition reaction of HNIW is determined by a logical choice method. The equations for calculating the critical temperatures of thermal explosion (T_b) and adiabatic time-to-explosion (t_TIad) based on Kooij formula are used to calculate the values of T_b and t_TIad to evaluate the thermal safety and heat-resistant ability of HNIW. All the original data needed for analyzing the kinetic parameters are from nonisothermal DSC curves. The results show that the kinetic model function in differential form and the values of E_a and A of decomposition reaction of HNIW are 3(1 − α)[−ln(1 − α)]^2/3, 152.73 kJ mol⁻¹ and 10^11.97 s⁻¹, respectively, and the values of self-accelerating decomposition temperature (T_SADT), T_b and t_TIad are 486.55 K, 493.11 K and 52.01 s, respectively.     

Estimating component characteristics from system failure‐time data

Suppose that failure times are available from a random sample of N systems of a given, fixed design with components which have i.i.d. lifetimes distributed according to a common distribution F. The inverse problem of estimating F from data on observed system lifetimes is considered. Using the known relationship between the system and component lifetime distributions via signature and domination theory, the nonparametric maximum likelihood estimator _N(t) of the component survival function (t) is identified and shown to be accessible numerically in any application of interest. The asymptotic distribution of _N(t) is also identified, facilitating the construction of approximate confidence intervals for (t) for N sufficiently large. Simulation results for samples of size N = 50 and N = 100 for a collection of five parametric lifetime models demonstrate the utility of the recommended estimator. Possible extensions beyond the i.i.d. framework are discussed in the concluding section. © 2010 Wiley Periodicals, Inc. Naval Research Logistics, 2010     

Structure design and property adjustment of new cage rich-nitrogen pentazolyltetraazacubanes as potential high energy density compounds

In this study, based on two attractive energetic compounds pentazole (PZ) and tetraazacubane (TAC), a new family of high energy and high nitrogen compounds pentazolyltetraazacubanes were designed. Then, a different number of NH₂ or NO₂ groups were introduced into the system to further adjust the property. The structures, properties, and the structure-property relationship of designed molecules were investigated theoretically. The results showed that all nine designed compounds have extremely high heat of formation (HOF, 1226-2734 kJ/mol), good density (1.73–1.88 g/cm³), high detonation velocity (8.30–9.35 km/s), high detonation pressure (29.8–39.7 GPa) and acceptable sensitivity (ΔV: 41-87 ų). These properties could be effectively positive adjusted by replacing one or two PZ rings by NH₂ or/and NO₂ groups, especially for the energy and sensitivity performance, which were increased and decreased obviously, respectively. As a result, two designed pentazolyltetraazacubanes were predicted to have higher energy and lower sensitivity than the famous high energy compound in use 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, while two others have better combination property than 1,3,5-Trinitro-1,3,5-triazacyclohexane. In all, four new pentazolyltetraazacubanes with good combination performance were successfully designed by combining PZ with TAC, and the further property adjustment strategy of introducing a suitable amount of NH₂/NO₂ groups into the system. This work may help develop new cage energetic compounds.     

热分析逸出气体氨的测定

用化学吸收光度法 (CAP)和热重 气相色谱联用法 (TG GC)测定了热分析逸出气中的氨。两种方法均简便、快捷和准确 ,通常回收率在 1 0 0± 6 %。比较了这些方法的使用范围     

On a sequential rule for estimating the location parameter of an exponential distribution

Let us assume that observations are obtained at random and sequentially from a population with density function In this paper we consider a sequential rule for estimating μ when σ is unknown corresponding to the following class of cost functions In this paper we consider a sequential rule for estimating μ when σ is unknown corresponding to the following class of cost functions Where δ(X_I,…,X_N) is a suitable estimator of μ based on the random sample (X₁,…, X_N), N is a stopping variable, and A and p are given constants. To study the performance of the rule it is compared with corresponding “optimum fixed sample procedures” with known σ by comparing expected sample sizes and expected costs. It is shown that the rule is “asymptotically efficient” when absolute loss (p=-1) is used whereas the one based on squared error (p = 2) is not. A table is provided to show that in small samples similar conclusions are also true.     

Special materials in pyrotechnics VII: Pyrotechnics used in thermal batteries

Thermal batteries are unique direct current (DC) electrical power sources with long shelf live, high reliability and higher power density than classical alkaline batteries. This paper gives a brief overview into the working principle of thermal batteries and reviews the properties of zirconium/barium chromate (Zr/BaCrO₄) pyrolant previously used as first fire and iron/potassium perchlorate (Fe/KClO₄) pyrolant (Heat), commonly applied as heating pellet in thermal batteries and its hazard properties. The review gives 64 references to the public domain. CAS-Nos. Zr: [7440-67-7], BaCrO₄: [10294-40-3], Fe: [7439-89-6], KClO₄: [7778-74-7], Viton: [9011-17-0].CAS-Nos. Zr: [7440-67-7], BaCrO₄: [10294-40-3], Fe: [7439-89-6], KClO₄: [7778-74-7], Viton: [9011-17-0].     

A general treatment of upper unbounded and bounded hitchcock problems

This paper is designed to treat (a) the problem of the determination of the absolute minimum cost, with the associated assignments, when there is no limit, N, on the number of parcels available for shipment in a modified Hitchcock problem. This is accomplished with the use of a transformed cost matrix. C*, to which the so-called transportation paradox does not apply. The general Hitchcock solution using C* gives the cost T*, which is the absolute minimum cost of the original problem, as well as sets of assignments which are readily transformed to give the general assignments of the original problem. The sum of these latter assignments gives the value of N_u, the unbounded N for minimum cost. In addition, this paper is designed to show (b) how the method of reduced matrices may be used, (c) how a particular Hitchcock solution can be used to determine a general solution so that one solution using C* can provide the general answer, (d) how the results may be modified to apply to problems with fixed N, and hence (e) to determine the function of the decreasing T as N approaches N_u, and finally (f) to provide a treatment when the supplies at origin i and/or the demands at destination j, are bounded.     

Cell structure of microcellular combustible object foamed by supercritical carbon dioxide

In order to solve the issue that the combustible objects for cased telescoped ammunition (CTA) didn't burn completely during the combustion process, the microcellular combustible objects were foamed with numerous cells in the micron order to improve the combustion performance by the supercritical carbon dioxide (SCCO₂) foaming technology. As the cell structure determined the combustion properties of microcellular combustible objects, the solubility of SCCO₂ dissolved into the combustible objects was obtained from the gravimetric method, and scanning electron microscope (SEM) was applied to characterize the cell structure under various process conditions of solubility, foaming temperature and foaming time. SEM images indicate that the cell diameter of microcellular combustible objects is in the level of 1 μm and the cell density is about 10¹¹ cell⋅cm⁻³. The microcellular combustible objects fabricated by the SCCO₂ foaming technology are smooth and uniform, and the high specific surface area of cell structure can lead to the significant combustion performance of microcellular combustible object for CTA in the future.