Plasma-assisted ignition and deflagration-to-detonation transition

Non-equilibrium plasma demonstrates great potential to control ultra-lean, ultra-fast, low-temperature flames and to become an extremely promising technology for a wide range of applications, including aviation gas turbine engines, piston engines, RAMjets, SCRAMjets and detonation initiation for pulsed detonation engines. The analysis of discharge processes shows that the discharge energy can be deposited into the desired internal degrees of freedom of molecules when varying the reduced electric field, E/n, at which the discharge is maintained. The amount of deposited energy is controlled by other discharge and gas parameters, including electric pulse duration, discharge current, gas number density, gas temperature, etc. As a rule, the dominant mechanism of the effect of non-equilibrium plasma on ignition and combustion is associated with the generation of active particles in the discharge plasma. For plasma-assisted ignition and combustion in mixtures containing air, the most promising active species are O atoms and, to a smaller extent, some other neutral atoms and radicals. These active particles are efficiently produced in high-voltage, nanosecond, pulse discharges owing to electron-impact dissociation of molecules and electron-impact excitation of N(2) electronic states, followed by collisional quenching of these states to dissociate the molecules. Mechanisms of deflagration-to-detonation transition (DDT) initiation by non-equilibrium plasma were analysed. For longitudinal discharges with a high power density in a plasma channel, two fast DDT mechanisms have been observed. When initiated by a spark or a transient discharge, the mixture ignited simultaneously over the volume of the discharge channel, producing a shock wave with a Mach number greater than 2 and a flame. A gradient mechanism of DDT similar to that proposed by Zeldovich has been observed experimentally under streamer initiation.     

Thermal reactivity of some nitro- and nitroso-compounds derived from 1,3,5,7-tetraazabicyclo[3.3.1]nonane at contamination by ammonium nitrate

Thermal reactivity of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT), 3,7-dinitroso-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DNPT), 1,3,5-trinitroso-1,3,5-triazinane (TMTA or R-salt), 1,3,5-trinitro-1,3,5-triazinane (hexogen or RDX), 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetrazocane (DADN), alpha-modification of the 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (octogen or HMX) and of their mixtures with 2wt.% of ammonium nitrate (AN) has been examined by means of non-isothermal differential thermal analysis. The resulting data were analyzed according to the Kissinger method. The reactivity was expressed as the E(a)R(-1) slopes of the Kissinger relationship. A relatively high reactivity has been found with mixtures of DPT and DNPT with AN. Electronic charges q(N) at nitrogen atoms in molecules of the compounds studied were calculated by means of ab initio DFT B3LYP/6-31G** method. The relationships were confirmed between the slopes E(a)R(-1) and the q(N) values for the nitrogen atoms primarily undergoing reaction. On the basis of these relationships it is stated that the destabilizing effect of AN is due to acidolytic attack of nitric acid (resulting from dissociation of ammonium nitrate) at the nitrogen atoms with the most negative q(N) values in the molecules of the compounds studied.     

Primary explosives: electrostatic discharge initiation, additive effect and its relation to thermal and explosive characteristics

All explosives, under all conditions must be considered vulnerable to generation, accumulation and discharge of static charge. The low energy static hazards of the order as low as 2-3 mJ need to be guarded against in case of highly sensitive compounds namely primary explosives. The hazard is normally associated with manufacturing and filling operations due to discharge of static charge accumulated on a person supplying energy up to 20 mJ. To reduce the risk associated with static initiation hazard in the processing and handling of the explosives, the electrostatic sensitivity tests can provide an important input regarding electrostatic hazards. This paper presents electrostatic sensitivity data in terms of zero ignition probability data (E(SE0)) of some of the initiatory explosives such as nickel/cobalt hydrazinium nitrate, silver azide, lead azide and mercury salt of 5-nitro tetrazole. Similar data has also been presented for samples coated with polyvinyl pyrrolidone to study its effect on electrostatic sensitivity. The electrostatic spark sensitivity of some conventional and novel made to explain the increased spark sensitivity behavior on the basis of the possible primary explosives has been studied. The electrostatic spark sensitivity of primary explosives decreased in the order of AgN3 = NHN > PbN6 > MNT > CoHN > BNCP. A possible correlation of spark energy with approximation and assumption has been drawn with thermal, detonation and mechanical properties. The polyvinyl pyrrolidone coated samples followed the same order but interestingly with increased spark sensitivity. An attempt has been reasoning of dielectric nature of the materials or exothermic effects of decomposition products of PVP. The present work also reports the electrostatic spark sensitivity of cap compositions.     

A new approach to predict the strength of high energy materials

This paper presents a new approach to predict the strength of energetic compounds in which there are important classes of high explosives including nitroaromatics, acyclic and cyclic nitramines, nitrate esters and nitroaliphatics. For C(a)H(b)N(c)O(d) compounds, the ratio of carbon to oxygen atoms and the predicted heat of detonation on the basis of the H(2)O-CO(2) arbitrary have been used to calculate the strength of an explosive. The new model can give good predictions for mentioned energetic compounds as determined by the Trauzl test. The novel correlation will be useful in predicting the strength or power of a new energetic compound that has significant potential in the field of explosives and propellants.     

Functionalization of terminal carbon atoms of hydroxyl terminated polybutadiene by polyazido nitrogen rich molecules

We report a novel synthetic approach for the attachment of the polyazido nitrogen rich molecule on to the hydroxyl terminated polybutadiene (HTPB) backbone. The terminal carbon atoms of the HTPB are functionalized by attaching cyanuric chloride (CYC) covalently on the HTPB backbone. Further reaction of this modified HTPB with sodium azide yields polyazido nitrogen rich HTPB. The unique physico-chemical properties and the microstructure of the HTPB do not get affected upon modification. IR, gel permeable chromatography (GPC) and absorption spectroscopy studies prove that the polyazido nitrogen rich molecules are covalently attached at the terminal carbon atoms of the HTPB. The π electron delocalization owing to long butadiene chain, strong electron withdrawing effect of the triazine molecules are the major driving forces for the covalent attachment of the triazine at the terminal carbon atoms of the HTPB. The disruption of the intermolecular hydrogen bonding between the terminal hydroxyl groups of the HTPB chains and the presence of hydrogen bonding between the N atoms of the triazine ring with OH group of the HTPB are observed. Theoretical study also reveals the existence of the hydrogen bonding between the OH and N. Theoretical calculation shows that the detonation performance of the polyazido nitrogen rich HTPB are very promising.     

半芳族共聚酰胺合成及表征

采用低温溶液法制备不同链长的均聚酰胺、交替共聚酰胺和嵌段共聚酰胺,探究反应条件对聚酰胺序列结构的影响.结果表明,红外可定性区分半芳族及脂肪族聚酰胺,二胺链节中间碳原子的13 C-NMR化学位移和峰裂分情况可用于鉴别不同碳链长度的均聚酰胺、交替共聚酰胺及嵌段共聚酰胺.交替共聚酰胺PA6T/66、PA4T/46和PA3T/...     

Some properties of explosive mixtures containing peroxides Part II. Relationships between detonation parameters and thermal reactivity of the mixtures with triacetone triperoxide

This study concerns mixtures of triacetone triperoxide (3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexoxonane, TATP) and ammonium nitrate (AN) with added water (W), as the case may be, and two dry mixtures of TATP with urea nitrate (UN). Relative performances (RP) of the mixtures and their individual components, relative to TNT, were determined by means of ballistic mortar. Thermal reactivity of these mixtures was examined by means of differential thermal analysis and the data were analyzed according to the modified Kissinger method (the peak temperature was replaced by the temperature of decomposition onset in this case). The reactivity, expressed as the EaR(-1) slopes of the Kissinger relationship, correlates with the squares of the calculated detonation velocities for the charge density of 1000 kg m(-3) of the studied energetic materials. Similarly, the relationships between the EaR(-1) values and RP have been found. While the first mentioned correlation (modified Evans-Polanyi-Semenov equation) is connected with the primary chemical micro-mechanism of the mixtures detonation, the relationships in the second case should be connected with the thermochemical aspects of this detonation.     

Performance evaluation of an in-injection port thermal desorption/gas chromatographic/negative ion chemical ionization mass spectrometric method for trace explosive vapor analysis

A gas chromatographic method utilizing thermal desorption of Tenax TA and sol-gel sorbent traps has been developed and validated for the analysis of trace explosive vapor with negative ion chemical ionization mass spectrometric detection. Sorbent tubes were packed with Tenax TA and sorbent particles prepared in-house by the sol-gel process. Thermal desorption was performed within a split/splitless injection port with minimal instrument modification. Performance was characterized by relative thermal desorption recovery, precision (reproducibility), linearity of the calibration, and method detection limits. Method validation was performed with a series of dinitrotoluenes, dinitrobenzene, trinitrotoluene, trinitrobenzene, two aminodinitrotoluenes, three nitroesters, and two nitramines. The performance of Tenax TA and the sol-gel sorbents is evaluated based on the method validation data. The method was applied to the analysis of trace explosive vapor collected and concentrated with sol-gel solid sorbent traps from the headspace of a smokeless gunpowder sample.     

B/N/Si掺杂的(9,0)型碳纳米管电子结构第一性原理研究

基于密度泛函理论(DFT)的DMol3软件包,研究了(9,0)型碳纳米管(CNT)顶端掺杂B/N/Si等元素对其几何结构及电子结构的影响.结果表明,掺杂原子对非掺杂区几何结构影响微弱;加电场后,各种掺杂CNT顶端局域态密度(LDOS)峰位向价带移动;B/N/Si掺杂不仅引起CNT费米能级(Ef)处LDOS增大,而且最低空轨道与最高占有轨道的差值(LUMO-HOMO)降低.由此可预期CNT顶端掺B/N/Si均有利于场致电子发射,且改善幅度依次增强.     

A detailed model for the decomposition of nitramines: RDX and HMX

A unified decomposition scheme for two very important cyclic nitramines used as primary explosives – RDX and HMX – has been constructed using ab initio Density Functional Theory (DFT) calculations. Molecular parameters such as vibrational frequencies and moments of inertia corresponding to the computed potential energy profile of unimolecular decomposition of these nitramines were then used to obtain the thermochemistry of all identified species and reaction rate constants of each individual channel. These primary decomposition reactions were then combined with: (i) important secondary reactions of the key reactive radical intermediates, such as CH₂NNO₂ (Methylene Nitramine MN), CH₂N, NO, NO₂, OH, etc.; (ii) existing nitramie reaction networks [33]. We have developed an improved mechanism for the detailed chemistry of nitramines which can be applied to combustion and detonation phenomena of this class of energetic materials. This revised version was published online in June 2006 with corrections to the Cover Date.     

Decomposition of some polynitro arenes initiated by heat and shock Part II: Several N-(2,4,6-trinitrophenyl)-substituted amino derivatives

Samples of 2,4,6-trinitroaniline (PAM), 2,4,6-trinitro-N-(2,4,6-trinitrophenyl)aniline (DPA), N,N'-bis(2,4,6-trinitrophenyl)-3,5-dinitropyridine-2,6-diamine (PYX) and N,N',N'-tris(2,4,6-trinitrophenyl)-1,3,5-triazine-2,4,6-triamine (TPM) were exposed to heat or to shock and then analysed chromatographically (LC-UV and LC/MS). It was found that the main identified decomposition products of these two incomplete initiations are identical for each of the compounds studied. It has been stated that the chemical micro-mechanism of the primary fragmentations of their low-temperature decomposition should be the same as in the case of their initiation by shock, including fragmentation during their detonation transformation.     

Detection of the 1H and 15N NMR resonances of sulfamate groups in aqueous solution: a new tool for heparin and heparan sulfate characterization

Sulfamate (NHSO(3)(-)) groups are critically important structural elements of the glycosaminoglycans heparin and heparan sulfate (HS). Experimental conditions are presented for detection of the sulfamate (1)H NMR resonances in aqueous solution. NMR spectra reported for N-sulfoglucosamine (GlcNS) and the synthetic pentasaccharide drug fondaparinux demonstrate the broad utility of the sulfamate group (1)H chemical shifts to reflect differences in molecular structure. The sulfamate protons also provide an efficient route for detection of (15)N chemical shifts through proton-nitrogen correlations measured with the heteronuclear single quantum coherence (HSQC) experiment. The HSQC spectra of GlcNS, fondaparinux, and the low-molecular weight heparin enoxaparin illustrate the power of the (1)H and (15)N chemical shifts of the sulfamate NH groups for the structural characterization of heparin and HS.     

Approximate prediction of melting point of nitramines, nitrate esters, nitrate salts and nitroaliphatics energetic compounds

A simple new procedure is introduced to predict melting point of selected class of energetic compounds containing nitramines, nitrate esters, nitrate salts and nitroaliphatics energetic compounds. The number of nitrogen and oxygen as well as the number of nitramine group and the contribution of some specific functional groups would be needed in the new method. Energetic compounds should contain at least one of the functional groups including N-NO(2), C-ONO(2) or nonaromatic C-NO(2). Calculated melting point for 33 nitramines, nitrate esters, nitrate salt and nitroaliphatics are compared with experimental data. Predicted melting points have average deviation of 5.4% for these energetic compounds.     

Flame acceleration and the development of detonation in fuel-oxygen mixtures at elevated temperatures and pressures

Experimental measurements of the conditions required for the development of detonation in a 7 mm tube following ignition by a low energy spark are reported. There are then compared to previous experimental propagation limit criterion using theoretical predictions of detonation cell sizes based on a one-dimensional detonation length scale computed using a detailed chemical kinetic scheme. Technical difficulties precluded direct cell size measurements. Ethylene-oxygen and hydrogen-methane-oxygen mixtures were investigated as well as methane-ammonia-oxygen, at initial pressures and temperatures in the ranges 1-7 bar and 293-540 K, respectively. The likelihood of detonation in ethylene-air mixtures in 150 mm and 50mm pipes at ambient initial conditions is also discussed in relation to published cell width data.The results indicate that whilst detonation cell width predictions do not provide a quantitative measure of the conditions for which detonation may develop in a pipe of given diameter, for prescribed initial conditions, predicted detonation cell size data does provide useful qualitative guidance as to possible hazardous compositions, particularly if preliminary experimental safety testing is thought to be necessary.     

1，3-二叠氮乙酰氧基-2，2-二叠氮甲基丙烷（PEAA）的结构、性能与热分解机理的理论研究磁

1,3-二叠氮乙酰氧基-2,2-二叠氮甲基丙烷（PEAA）是一种玻璃态转化温度低而含氮量高的叠氮化物,具有作为含能增塑剂的潜在应用价值。文中采用密度泛函理论研究了其分子结构和红外光谱,预测了热力学函数、生成焓、爆轰性能和比冲;采用分子力学方法预测了其晶体结构和晶体密度;计算了多种可能的热解引发键的键解离能。结果表明,PEAA的热分解始于乙酰氧基上叠氮基的N—N键断裂,该过程经氢转移过渡态完成并放出氮气和热量,所需活化能约162kJ／mol。与已有实际应用的叠氮增塑剂DATH（1,7-二叠氮基-2,4,6-三硝基-2,4,6-三氮杂庚烷）相比,PEAA的热稳定性更好。还考察了PEAA对硝胺改性双基推进剂能量性能的影响,发现无论用PEAA替代其中的NG还是RDX均使体系的能量输出和比冲增大,但体系的爆速和爆压略有降低。     

Some characteristics of 3,7-dinitro-, 3,7-dinitroso- and dinitrate compounds derived from 1,3,5,7-tetraazabicyclo[3.3.1]nonane

The paper presents a set of some literature data and the authors' own experimental results of stability, sensitivity and explosion parameters of energetic Mannich N-bases, 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT), 3,7-dinitroso-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DNPT) and hexamethylenetetramine dinitrate (HEXADI). Both their chemical and thermal reactivities are discussed. The results of small-scale cook-off test, determination of initiation ability, detonation velocity, impact sensitivity and performance show that the lowest process safety risks are connected with HEXADI.     

Formation of soot from polycyclic aromatic hydrocarbons as well as fullerenes and carbon nanotubes in the combustion of hydrocarbon

The eightieth anniversary of Academician, Lenin Prize Winner Rem Ivanovich Soloukhin is an important event for the scientific association of investigators of combustion and detonation processes. R. I. Soloukhin has developed original gasdynamic laser systems based on the selective thermal excitation and mixing in a supersonic flow: efficient high-power gas-flow lasers of convective type with electric excitation and chemical lasers initiated by an electron beam. He proposed methods of measuring the rapidly changing pressure, density, temperature, and other parameters of processes occurring in shock waves.     

圆周速度对碳纳米管-银-石墨复合材料接触电压降的影响

采用粉末冶金方法制备碳纳米管-银-石墨复合材料,研究圆周速度对复合材料接触电压降的影响.结果表明,当压力一定时,随着圆周速度的增大,复合材料的接触电压降略有增加,而圆周速度增大到一定值后,接触电压降急剧增加并伴有火花磨损出现.压力较小时(1N/cm2)圆周速度为7.5m/s时就出现电火花,压力较大时(2.5N/cm2)圆周速度为15m/s出现电火花.在圆周速度不变的条件下,接触电压降先升后降最后趋于稳定.     

Theoretical prediction of condensed phase heat of formation of nitramines, nitrate esters, nitroaliphatics and related energetic compounds

An empirical approach is presented for calculation heats of formation of nitramines, nitrate esters, nitroaliphatics and related energetic compounds which contain at least one of the functional groups including N-NO(2), C-ONO(2) or nonaromatic C-NO(2). This approach is based on elemental composition and various structural and functional group parameters of C(a)H(b)N(c)O(d) energetic compounds. Heat of formation for 78 nitrocompounds including nitramines, nitrate esters, nitroaliphatics and the data obtained is compared with experimental data. Root mean square (rms) of deviation for 19 well known of mentioned energetic compounds are also compared with complex quantum mechanical computations which show 23.8 and 21.3 kJ/mol for new and quantum mechanical methods, respectively. Predicted condensed phase heats of formation for remainder 59 energetic molecules with complex molecular structures have a rms deviation from experiment of 42.3 kJ/mol.     

Formation of an overdriven detonation wave in the flow of methane–oxygen mixtures in a variable cross section channel

The formation of an overdriven detonation wave in methane-oxygen mixtures in an axially symmetrical channel with a variable cross section was experimentally investigated. The ignition of gas mixture was carried out using the spark gap, located at the closed end of the channel. To create the overcompressed shock detonation wave, the decay of the stationary detonation wave was performed at the transition to the channel of a larger cross section. The created complex of shock wave and flame front, moving behind it, propagated in a channel with conical narrowing. The formation of the overdriven detonation wave, with parameters exceeding the parameters of Chapman–Jouguet stationary detonation by a few times, was registered at the outlet of conical narrowing. The rates and pressures on the front of the detonation wave were determined, depending on the mixture composition. The sizes of detonation cells, diagrams of compression waves propagation, flame front, and detonation wave in a combustion chamber, depending on the mixture composition, were presented.