Detonation Velocities and Pressures,and their Relationships with Electric Spark Sensitivities for Nitramines

The DFT‐B3LYP method, with basis set 6–31G*, is employed to optimize molecular geometries and electronic structures of eighteen nitramines. The averaged molar volume (V) and theoretical density (ρ) are estimated using the Monte‐Carlo method based on 0.001 electrons/bohr³ density space. Subsequently, the detonation velocity (D) and pressure (P) of the explosives are estimated by using the Kamlet‐Jacobs equation on the basis of the theoretical density and heat of formation (Δ_fH), which is calculated using the PM3 method. The reliability of this theoretical method and results are tested by comparing the theoretical values of ρ and D with the experimental or referenced values. The theoretical values of D and P are compared with the experimental values of electric spark sensitivity (E_ES). It is found that for the compounds with metylenenitramine units ( CH₂N(NO₂) ) in their molecules (such as ORDX, AcAn and HMX) or with the better symmetrical cyclic nitramines but excluding metylenenitramine units (such as DNDC and TNAD), there is a excellent linear relationship between the square of detonation velocity (D²) or the logarithm of detonation pressure (lg P) and electric spark sensitivity (E_ES). This suggests that in the molecular design of energetic materials, such a theoretical approach can be used to predict their E_ES values, which have been proven to be difficult to predict quantitatively or to synthesize.     

A New General Correlation for Predicting Impact Sensitivity of Energetic Compounds

This paper describes an improved simple model for prediction of impact sensitivity of different classes of energetic compounds containing nitropyridines, nitroimidazoles, nitropyrazoles, nitrofurazanes, nitrotriazoles, nitropyrimidines, polynitroarenes, benzofuroxans, polynitroarenes with α‐CH, nitramines, nitroaliphatics, nitroaliphatic containing other functional groups, and nitrate energetic compounds. The model is based on some molecular structural parameters. It is applied for 90 explosives, which have different molecular structures. The predicted results are compared with outputs of complex neural network approach as one of the best available methods. Root mean squares (rms) of deviations of different energetic compounds are 24 and 49 cm, corresponding to 5.88 and 12.01 J with 2.5 kg dropping mass, for new and neural network methods, respectively. The novel model also predicts good results for eight new synthesized and miscellaneous explosives with respect to experimental data.     

Properties of CP: Coefficient of Thermal Expansion,Decomposition Kinetics,Reaction to Spark,Friction and Impact

The properties of pentaamine (5‐cyano‐2H‐tetrazolato‐N2) cobalt (III) perchlorate (CP), which was first synthesized in 1968, continues to be of interest for predicting behavior in handling, shipping, aging, and thermal cook‐off situations. We report coefficient of thermal expansion (CTE) values over four specific temperature ranges, decomposition kinetics using linear and isothermal heating, and the reaction to three different types of stimuli: impact, spark, and friction. The CTE was measured using a Thermal Mechanical Analyzer (TMA) for samples that were uniaxially compressed at 68.95 MPa and analyzed over a dynamic temperature range of −20 °C to 70 °C. Differential scanning calorimetry, DSC, was used to monitor CP decomposition at linear heating rates of 1–7 °C min⁻¹ in perforated pans and of 0.1–1.0 °C min⁻¹ in sealed pans. The kinetic triplet was calculated using the LLNL code Kinetics05, and predictions for 210 °C and 240 °C are compared to isothermal thermogravimetric analysis (TGA) experiments. Values are also reported for spark, friction, and impact sensitivity.     

废弃电子设备中塑料的回收利用

综述了近年来国内外废弃电子设备中塑料回收利用现状。着重介绍机械回收、化学回收和能量回收等资源化技术;讨论了存在的问题和研究发展方向。     

Relationship Between the Electrostatic Sensitivity of Nitramines and Their Molecular Structure

In this paper, a new approach is introduced to predict the electrostatic sensitivity of nitramines on the basis of their molecular structure. The ratio of carbon to oxygen and the existence of two specific structural parameters can be used for the prediction of the electrostatic sensitivity of nitramines. The results are also compared with quantum mechanical computations from [9] so that the new method gives better predictions with respect to the measured data. Electrostatic sensitivities calculated by the new method for two new nitramines CL‐20 [2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane] and TNAZ [1,3,3‐trinitroazatidine] are also close to the experimental data.     

电场作用下磺化聚苯乙烯微球在弹性体中梯度结构构建及性能研究

先采用硫酸对聚苯乙烯微球经过磺化得到带正电荷的磺化聚苯乙烯(s PS),将s PS分散在聚二甲基硅氧烷(PDMS)预聚体中,在高压直流电场下通过电泳作用形成梯度结构,再通过PDMS的热固化后将梯度结构固定下来。采用马尔文Zeta电位仪分析了s PS微球电荷,扫描电镜(SEM)对s PS以及s PS/PDMS梯度膜的结构进行表征,动态热机械分析仪测试了材料的动态力学行为和介电损耗。结果表明,电压强度为500 V/mm时,s PS能够在PDMS预聚体中通过电泳作用形成梯度结构,s PS总质量分数为20%时,s PS/PDMS梯度膜相比相同组成的均匀膜断裂伸长率提高了9. 41%,损耗因子在所测得温度范围(-70~200℃)均提高。在s PS的玻璃化转变温度附近,s PS/PDM S梯度膜比均匀膜损耗因子提高了30%。进一步对梯度结构膜力学行为及介电损耗增强效应进行了详细分析。     

Calculation of Detonation Velocity,Pressure, and Electric Sensitivity of Nitro Arenes Based on Quantum Chemistry

The DFT‐B3LYP method, with basis set 6‐31G*, is employed to optimize molecular geometries and electronic structures of thirty‐nine nitro arenes. The averaged molar volume (V) and theoretical density (ϱ) are estimated using the Monte‐Carlo method, based on 0.001 electrons/bohr³ density space and a self‐compiled program. The detonation velocity (D) and pressure (P) of the explosives are estimated by using the Kamlet–Jacbos equation on the basis of the theoretical density and heat of formation (Δ_fH), which is calculated using the PM3 method. The reliability of this theoretical method and results are tested by comparing the theoretical values of ϱ and D with the experimental or referenced values. The theoretical values of D and P are correlated with the experimental values of electric sensitivity (E_ES). It is found that, for the nitro arenes, there is a linear relationship between the square of detonation velocity (D²) or detonation pressure (P) and electric sensitivity (E_ES), which suggests that such a theoretical approach can be used to predict or judge the magnitude of E_ES, which is difficult to measure in the molecular design of energetic materials. In addition, we have discussed the influence of the substituted groups and the parameters of the electronic structure on density, detonation velocity, pressure, and electric sensitivity, and have shown that the substituted groups have the effect of activity or insensitivity, and that the influence of Q_‐NO2 and E_LUMO is important.     

Selection and Synthesis of Energetic Heterocyclic Compounds Suitable for Use in Insensitive Explosive and Propellant Compositions

The rationale behind developing insensitive energetic compounds (IECs) for incorporation into insensitive munition (IM) formulations (rather than the alternative approach of desensitizing higher energy but sensitive compounds) is discussed. With the aim of selecting a maximum of 2–3 IECs suitable for use in insensitive explosive and propellant compositions, a survey of the literature on IECs published in the last 20 years was carried out. From around 50 candidates, a selection was made of eight prime candidates, all heterocyclic compounds (principally monocyclic or fused‐ring bicyclic compounds of the di‐ or triazine, triazole or oxadiazole classes), which displayed explosive performance significantly better than that of the ubiquitous IEC, TATB. The criteria for inclusion of compounds in these listings are described. Screening of the eight candidate compounds against further performance criteria reduced the list to five compounds which were evaluated in detail – these were: CL‐14 (5,7‐diamino‐4,6‐dinitrobenzofuroxan), ANPZ‐i (2,5‐diamino‐3,6‐dinitropyrazine), NNHT (2‐nitrimino‐5‐nitro‐hexahydro‐1,3,5‐triazine), NTAPDO (5‐nitro‐2,4,6‐triaminopyrimidine‐1,3‐dioxide), and PANT [4‐(picrylamino)‐5‐nitro‐1,2,3‐triazole]. A detailed analysis of scale‐up issues associated with each compound was then made, including cost and availability of precursors, hazards (chemical and explosive), effluent streams, and other scale‐up issues (e.g. materials of plant construction). A further downselection using these criteria gave the present short‐list comprising three compounds (the first three listed above) and further evaluation is in progress. The results of this study, funded by UK MOD, comprise the UK contribution to a nine‐nation European research collaboration in the EUCLID Common European Priority Area 14 “Energetic Materials”, as part of a five‐year project which commenced in October 2003.     

The Facile Synthesis and Energetic Properties of an Energetic Furoxan Lacking Traditional “Explosophore” Moieties: (E,E)‐3,4‐bis(oximomethyl)furoxan (DPX1)

Energetic furoxan (E,E)‐3,4‐bis(oximomethyl)furoxan (DPX1) was synthesized in 75 % yield, using a literature procedure, from a precursor readily available in one step from nitromethane. DPX1 was characterized for the first time as an energetic material in terms of calculated performance (V_det = 8245 m s⁻¹; p_C‐J = 29.0 GPa) and measured sensitivity (impact: 10 J; friction: 192 N; T_dec: 168 °C). DPX1 exhibits a sensitivity less than that of RDX, and a performance significantly higher than 2,4,6‐trinitrotoluene (TNT).     

UHT脱脂纯牛奶感官评价和电子鼻分析相关性研究

选取四种市售不同品牌的UHT脱脂纯牛奶作为研究对象,通过感官描述性分析和电子鼻技术对其风味属性进行评价。采用主成分分析(PCA)和聚类分析(CA)结合偏最小二乘回归法(PLSR)法将电子鼻传感器性能和感官属性进行相关性分析。结果表明样品奶油味及脂质感评分均较低;电子鼻的十个传感器对四个样品的区分效果良好;基于感官属性和传感器响应值的PLSR分析建立的相关性模型,能够很好地解释感官属性和传感器响应值的相关性,反映脱脂纯牛奶样品的整体信息。本文结合两种技术方法,弥补了人工感官评价存在的主观性与智能感官分析的局限性影响,旨在为后续改善脱脂纯牛奶风味提供技术参考。     

On the Correlation between Miscibility and Solubility Properties of Energetic Plasticizers/Polymer Blends: Modeling and Simulation Studies

In this paper, systems for which miscibility (hydroxyl‐terminated polybutadiene–dioctyl adipate or HTPB–DOA) or immiscibility (HTPB–diethylene glycol dinitrate or HTPB–DEGDN) have been firmly established were used to test the usefulness of an atomistic molecular mechanics model. Two specific aspects were discussed: miscibility assessment of a plasticizer/polymer blend, and predictions of the enthalpy of vaporization. Simulations were carried out using Amorphous Cell and Discover packages of the Material Studio software using Compass force field for all calculations. A good agreement has been found for miscibility observations of blends, and for solubility parameter, density, and derived enthalpy of vaporization for pure substances. Therefore, the approach proposed in this work is a useful tool to provide insights on miscibility and properties of a given polymer/plasticizer blend. In addition, it is a promising technique to help in screening among several plastic bonded explosive (PBX) formulations prior to real experimental tests.     

Effect of Electronic Properties of Catalysts for the Oxidative Coupling of Methane on Their Selectivity and Activity

The oxidative coupling of methane (OCM) to higher hydrocarbons may eventually become an interesting alternative for the chemical utilization of natural gas. Extensive studies have been conducted since the works of Keller and Bhasin [l] and of Hinsen and Baerns [2].     

Theoretical Electronic Structure and Properties of Alternating Fluorene–Acceptor Conjugated Copolymers and Their Model Compounds

The theoretical geometries and electronic properties of fluorene (F) based alternating donor–acceptor conjugated copolymers and their model compounds were studied by the density function theory (DFT) at the B3LYP level with 6–31G or 6–31G** basis set. The acceptors investigated in this study include thiazole (TZ), thiadiazole (TD), thienopyrazine (TP), thienothiadiazole (TT), thiadiazolothienopyrazine (TTP), quinoxaline (Q), benzothiadiazole (BT), pyrazinoquinoxaline (PQ), thiadiazoloquinoxaline (TQ), and benzobisthiathiadiazole (BB). The torsional angle, bridge bond length, bond length alternation, and intramolecular charge transfer were simulated and correlated with the electronic properties, i.e., HOMO, LUMO level, and band gap. The geometries of fluorene-based donor–acceptor alternating copolymers and their model compounds are significantly affected by the structure of acceptors, particularly the ring size on the backbone. The electronic properties of the polymers and their model compounds are well correlated with the acceptor strength, coplanarity of the backbone, and intramolecular charge transfer. The theoretical study suggests that the electronic properties of alternating fluorene–acceptor conjugated copolymers could be tuned by the geometries or acceptor strength. Hence, these proposed copolymers could have potential applications as light-emitting diodes (LEDs), transparent conductor, or photovoltaic devices.     

Effect of Electronic Properties of Catalysts for the Oxidative Coupling of Methane on Their Selectivity and Activity

The oxidative coupling of methane (OCM) to higher hydrocarbons may eventually become an interesting alternative for the chemical utilization of natural gas. Extensive studies have been conducted since the works of Keller and Bhasin [l] and of Hinsen and Baerns [2].     

HDPE树脂流变参数与分子量分布的关系研究

测定了4种高密度聚乙烯(HDPE)树脂的分子量及其分布,研究了其毛细管流变行为和动态流变行为,并分析了得到的流变参数和分子量分布的关系。结果表明:仅在较低挤出速度或较高温度条件下,用毛细管流变测得的非牛顿指数才能用作分子量分布的量度;用动态流变测得的剪切变稀指数、流变多分散指数、幂率指数均可在一定程度上反映了HDPE树脂分子量分布的大小,其中幂率指数与分子量分布的相关性最好(相关系数r2=0.994)。     

Investigation of the Correlations Between Nitro Group Charges and Some Properties of Nitro Organic Compounds

The so‐called nitro group charge method (NGCM) is successfully established to investigate some properties of nitro compounds including the molecular stability measured by total energy (only for isomers), the bond lengths, bond dissociation energies (BDE), and the nitrating activities, in that the method considers the molecular structure. These properties are intrinsically and especially thermodynamically consistent with each other and can be well related qualitatively and even quantitatively with nitro group charges (Q_Nitro). The correlations between Q_Nitro and the properties are: (1) for nitro isomers, the more negative the average Q_Nitro, the lower the total energy and the more stable is the isomer; (2) for any separate group of nitro compounds, the more negative Q_Nitro, the shorter the R‐nitro bond length; (3) for the bond dissociation energy, more negative Q_Nitro corresponds to a higher BDE of the R‐nitro bond; (4) by NGCM, the conditions, the reaction rates and the occurrence ratios of products of some nitration can be predicted and compared: the more negative Q_Nitro of the product, the easier and faster the nitration, and the higher the occurrence ratio of the corresponding product.     

The energetic and electronic properties of atomic hydrogen on MgO(001) surface: Tight-binding and Ab initio calculations

We report the computational results of hydrogen adsorption atop Mg and O atoms on the MgO(001) surface, followed by its absorption under the target atoms, using two approaches: tight-binding and ab initio methods. We present the energetic and electronic aspects of these interactions and discuss the qualities of the non-self-consistent field tight-binding results compared with the ab initio results. There is the qualitative reproduction of ab initio results in the hydrogen adsorption phase on both types of ions. The tight-binding results are found to be more accurate in the hydrogen absorption phase than in the adsorption phase. In the adsorption calculations the introduction of the surface dipole term in the tight-binding total energy would be required to compensate for the absence of electronic relaxation in the MgO(001) surface.     

Molecular Dynamics Simulations of Polymer‐Bonded Explosives (PBXs): Modeling,Mechanical Properties and their Dependence on Temperatures and Concentrations of Binders

Two models, i.e. “covering” and “cutting” models, for the polymer‐bonded explosives (PBXs) were proposed for different researching aspects. Used for choosing polymeric binders, the “covering” models are mainly applied to find the relations of temperatures and concentrations respectively with elastic properties of the PBXs. The “cutting” model is especially used to describe the highly anisotropic behavior of 1,3,5‐triamino‐2,4,6‐trinitrobenzene crystals (TATB). These models were realized by using molecular dynamics methods. It is found that the ductility of crystalline TATB can be effectively improved by blending fluorine‐containing polymers in small amounts. The moduli for the PBXs decrease with increase in temperature and concentration of binders. Different crystalline surfaces interacting with the same polymer binder have different modulus‐decreasing effects due to the highly anisotropic behavior of TATB. The modulus‐decreasing effect for different crystalline surfaces ranking order is (010)≈(100)>(001).     

炸药的加速金属能力与分子结构关系的探讨

根据炸药分子结构的特点,应用量子力学原理和化学动力学的观点,探讨了炸药的分子结构与其在爆轰过程中能量释放速率之间的关系及炸药的分子结构与其加速金属能力之间的关系,发现共轭炸药具有能量释放快的特点,非共轭炸药具有持续加速金属的特性,高能量和能量释放快是炸药具有优越加速能力的必要条件,高能量、高密度共轭炸药是值得探索的一类炸药。