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.     

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.     

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。     

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.     

Neural network modeling to evaluate the dynamic flow stress of high strength armor steels under high strain rate compression

An artificial neural network (ANN) constitutive model is developed for high strength armor steel tempered at 500 °C, 600 °C and 650 °C based on high strain rate data generated from split Hopkinson pressure bar (SHPB) experiments. A new neural network configuration consisting of both training and validation is effectively employed to predict flow stress. Tempering temperature, strain rate and strain are considered as inputs, whereas flow stress is taken as output of the neural network. A comparative study on Johnson–Cook (J–C) model and neural network model is performed. It was observed that the developed neural network model could predict flow stress under various strain rates and tempering temperatures. The experimental stress–strain data obtained from high strain rate compression tests using SHPB, over a range of tempering temperatures (500–650 °C), strains (0.05–0.2) and strain rates (1000–5500/s) are employed to formulate J–C model to predict the high strain rate deformation behavior of high strength armor steels. The J-C model and the back-propagation ANN model were developed to predict the high strain rate deformation behavior of high strength armor steel and their predictability is evaluated in terms of correlation coefficient (R) and average absolute relative error (AARE). R and AARE for the J–C model are found to be 0.7461 and 27.624%, respectively, while R and AARE for the ANN model are 0.9995 and 2.58%, respectively. It was observed that the predictions by ANN model are in consistence with the experimental data for all tempering temperatures.     

Decomposition algorithms for minimal cut problems

Consider a network G(N. A) with n nodes, where node 1 designates its source node and node n designates its sink node. The cuts (Z_i, =), i= 1…, n - 1 are called one-node cuts if 1 ? Z_i,. n q Z_i, Z₁-_? {1}, Z_i ? Z_i+1 and Z_i and Z_i+l differ by only one node. It is shown that these one-node cuts decompose G into 1 m n/2 subnetworks with known minimal cuts. Under certain circumstances, the proposed one-node decomposition can produce a minimal cut for G in 0(n² ) machine operations. It is also shown that, under certain conditions, one-node cuts produce no decomposition. An alternative procedure is also introduced to overcome this situation. It is shown that this alternative procedure has the computational complexity of 0(n³).     

Graph distance‐dependent labeling related to code assignment in computer networks

For nonnegative integers d₁, d₂, and L(d₁, d₂)‐labeling of a graph G, is a function f : V(G) → {0, 1, 2, …} such that |f(u) − f(v)| ≥ d_i whenever the distance between u and v is i in G, for i = 1, 2. The L(d₁, d₂)‐number of G, λ(G) is the smallest k such that there exists an L(d₁, d₂)‐labeling with the largest label k. These labelings have an application to a computer code assignment problem. The task is to assign integer “control codes” to a network of computer stations with distance restrictions, which allow d₁ ≤ d₂. In this article, we will study the labelings with (d₁, d₂) ∈ {(0, 1), (1, 1), (1, 2)}. © 2004 Wiley Periodicals, Inc. Naval Research Logistics, 2005     

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.     

Deterministic and stochastic scheduling with teamwork tasks

We study a class of new scheduling problems which involve types of teamwork tasks. Each teamwork task consists of several components, and requires a team of processors to complete, with each team member to process a particular component of the task. Once the processor completes its work on the task, it will be available immediately to work on the next task regardless of whether the other components of the last task have been completed or not. Thus, the processors in a team neither have to start, nor have to finish, at the same time as they process a task. A task is completed only when all of its components have been processed. The problem is to find an optimal schedule to process all tasks, under a given objective measure. We consider both deterministic and stochastic models. For the deterministic model, we find that the optimal schedule exhibits the pattern that all processors must adopt the same sequence to process the tasks, even under a general objective function GC = F(f₁(C₁), f₂(C₂), … , f_n(C_n)), where f_i(C_i) is a general, nondecreasing function of the completion time C_i of task i. We show that the optimal sequence to minimize the maximum cost MC = max f_i(C_i) can be derived by a simple rule if there exists an order f₁(t) ≤ … ≤ f_n(t) for all t between the functions {f_i(t)}. We further show that the optimal sequence to minimize the total cost TC = ∑ f_i(C_i) can be constructed by a dynamic programming algorithm. For the stochastic model, we study three optimization criteria: (A) almost sure minimization; (B) stochastic ordering; and (C) expected cost minimization. For criterion (A), we show that the results for the corresponding deterministic model can be easily generalized. However, stochastic problems with criteria (B) and (C) become quite difficult. Conditions under which the optimal solutions can be found for these two criteria are derived. © 2004 Wiley Periodicals, Inc. Naval Research Logistics, 2004     

Quantification of projection angle in fragment generator warhead

Tactical Ballistic Missile (TBM) class target neutralization by the fragment spray of a Fragment Generator Warhead (FGW) calls for quantification of fragment projection angle scatter to finalize the end game engagement logic. For conventional axi-symmetric warhead, dispersion is assumed to be normal with a standard deviation of 3⁰. However, such information is not available in case of FGW. Hence, a set of experiments are conducted to determine the dispersion of fragments. The experiments are conducted with a specific configuration of FGW in an identical arena to quantify the scatter and then verified its applicability to other configurations having a range of L/D and C/M ratios, and contoured fragmenting discs. From the experimental study, it is concluded that the scatter in projection angle follows normal distribution with a standard deviation of 0.75° at Chi-square significance level of 0.01(χ²_0.99).     

Studies on the flame propagation characteristic and thermal hazard of the premixed N2O/fuel mixtures

An experimental study was carried out to investigate the flame propagation and thermal hazard of the premixed N₂O/fuel mixtures, including NH₃, C₃H₈ and C₂H₄. The study provided the high speed video images and data about the flame locations, propagation patterns, overpressures and the quenching diameters during the course of combustion in different channels to elucidate the dynamics of various combustion processes. The onset decomposition temperature was determined using high-performance adiabatic calorimetry. It was shown that the order of the flame acceleration rate and thermal hazard was N₂O/C₂H₄>N₂O/C₃H₈>N₂O/NH₃.     

On scheduling a single machine to minimize a piecewise linear objective function: A compact MIP formulation

We study the scheduling situation in which a set of jobs subjected to release dates and deadlines are to be performed on a single machine. The objective is to minimize a piecewise linear objective function ∑_jF_j where F_j(C_j) corresponds to the cost of the completion of job j at time C_j. This class of function is very large and thus interesting both from a theoretical and practical point of view: It can be used to model total (weighted) completion time, total (weighted) tardiness, earliness and tardiness, etc. We introduce a new Mixed Integer Program (MIP) based on time interval decomposition. Our MIP is closely related to the well‐known time‐indexed MIP formulation but uses much less variables and constraints. Experiments on academic benchmarks as well as on real‐life industrial problems show that our generic MIP formulation is efficient. © 2009 Wiley Periodicals, Inc. Naval Research Logistics, 2009     

Scheduling deteriorating jobs to minimize makespan

We consider a single-machine problem of scheduling n independent jobs to minimize makespan, in which the processing time of job J_j grows by w_j with each time unit its start is delayed beyond a given common critical date d. This processing time is p_j if J_j starts by d. We show that this problem is NP-hard, give a pseudopolynomial algorithm that runs in time and O(nd) space, and develop a branch-and-bound algorithm that solves instances with up to 100 jobs in a reasonable amount of time. We also introduce the case of bounded deterioration, where the processing time of a job grows no further if the job starts after a common maximum deterioration date D > d. For this case, we give two pseudopolynomial time algorithms: one runs in O(n²d(D − d) time and O(nd(D − d)) space, the other runs in p_j)²) time and p_j) space. © 1998 John Wiley & Sons, Inc. Naval Research Logistics 45: 511–523, 1998     

An absolute approximation algorithm for scheduling unrelated machines

Non‐preemptive scheduling of n independent jobs on m unrelated machines so as to minimize the maximal job completion time is considered. A polynomial algorithm with the worst‐case absolute error of min{(1 ? 1/m)p_max, p} is presented, where p_max is the largest job processing time and p is the mth element from the non‐increasing list of job processing times. This is better than the earlier known best absolute error of p_max. The algorithm is based on the rounding of acyclic multiprocessor distributions. An O(nm²) algorithm for the construction of an acyclic multiprocessor distribution is also presented. © 2006 Wiley Periodicals, Inc. Naval Research Logistics, 2006     

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.     

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.     

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。     

On labeling the vertices of products of complete graphs with distance constraints

Variations of Hale's channel assignment problem, the L(j, k)‐labeling problem and the radio labeling problem require the assignment of integers to the vertices of a graph G subject to various distance constraints. The λ_j,k‐number of G and the radio number of G are respectively the minimum span among all L(j, k)‐labelings, and the minimum span plus 1 of all radio labelings of G (defined in the Introduction). In this paper, we establish the λ_j,k‐number of ∏ K for pairwise relatively prime integers t₁ < t₂ < … < t_q, t₁ ≥ 2. We also show the existence of an infinite class of graphs G with radio number |V(G)| for any diameter d(G). © 2003 Wiley Periodicals, Inc. Naval Research Logistics, 2005     

Sandwich structure for enhancing the interface reaction of hexanitrohexaazaisowurtzitane and nanoporous carbon scaffolds film to improve the thermal decomposition performance

Improving the thermal decomposition performance of hexanitrohexaazaisowurtzitane (CL-20) by appropriate methods is helpful to promote the combustion performance of CL-20-based solid propellants. In this study, we synthesized a sandwich structure of CL-20 and nanoporous carbon scaffolds film (NCS) and emphatically studied the thermal decomposition performance of the composite structure. Thermogravimetric analysis and differential scanning calorimetry were used to measure the thermal decomposition process of the composite structure. The kinetic parameters of thermal decomposition were calculated by the thermal dynamic analysis software AKTS. These results showed that the thermal decomposition performance of the sandwich structure of CL-20 and NCS was better than CL-20. Among the tested samples, NCS with a pore size of 15 nm had the best catalytic activity for the thermal decomposition of CL-20. Moreover, the thermal decomposition curve of the composite structure at the heating rate of 1 K/min was deconvoluted by mathematical method to study the thermal decomposition process. And a possible catalytic mechanism was proposed. The excellent thermal decomposition performance is due to the sandwich structure enhances the interface reaction of CL-20 and NCS. This work may promote the extensive use of CL-20 in the field of solid rocket propellant.