Friction Sensitivity of Nitramines. Part Ⅰ:Comparison with Impact Sensitivity and Heat of Fusion

Fractions of β-HMX(β-1,3,5,7-tetranitro-1,3,5,7-tetrazocane) have been used to demonstrate the mutual relationship between friction and impact sensitivities.Inclusion of an additional twelve nitramines into this scenario resulted in a series of partial relationships,which were determined from the molecular structure of these substances.It was also found that there is a relation between increasing heats of fusion of the nitramines studied and their decreasing friction sensitivities.Comparison of friction sensitivity with heats of fusion,ΔHm,tr of the studied nitramines shows that the increase in ΔHm,tr values is more or less connected with a decrease in friction sensitivity.

多硝基化合物的静电火花感度与热分解参数的关联(英文)

通过测定 53种多硝基化合物在 50 %发火概率下的静电火花感度EES,发现由Skinner等人在热分解速率常数k =10 3s- 1 下建立的EES与温度倒数的半对数关系表达式随着化合物种类的不同而不同。分析结果表明 ,含能材料初始热分解的化学机理及其晶体中分子的相互作用对电火花点火起决定性的作用。

Crystal lattice free volume in a study of initiation reactivity of nitramines:Impact sensitivity

More detailed analysis of a mutual relationship of impact sensitivity(detected by sound) and crystal lattice free volume, △V, for the 18 nitramines shows that its course is not unequivocal. For a part of the studied compounds this sensitivity has increased with increase of the AV values, but for fairly big number of nitramines the relationship works in the opposite direction, especially for data of 1,3,5-trinitro-1,3,5-triazinane, 1,3,5,7-tetranitro-1,3,5,7-tetrazocane. and β-and ε-polymorphs of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane. Initiation reactivity of technical ε-polymorph of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane gives the impression by disorderliness in distribution of the actions of forces in its crystal lattice in comparison with its RS(reduced sensitivity) or chemically pure analogue. Limitations of partial shapes of the mentioned relationship by the molecular-structural similarity, and already published information about the decisive factors governing the crystal structure, signalizes a higher influence of the intermolecular interactions in a crystal lattice in comparison with influence of the crystal lattice free volume for initiation of the crystalline EMs.

Crystal lattice free volume in a study of initiation reactivity of nitramines:Friction sensitivity

The relationship between friction sensitivity(FS) and the crystal lattice free space per molecule, △V. of thirteen nitramines is described by a linear equation, divided into a number of the partial relationships with strong limitations by their molecular structure characteristics. Increasing FS due to raising of the △V values is not clearly confirmed. The influence of the △V values on friction sensitivity of nitramines is similar to that of their aza atoms which influence the mutual orientations of nitro groups in neighboring molecules. The dipole-dipole interaction of the oxygen and nitrogen atoms of nitro groups in neighboring nitramine molecules has a major effect on their own FS. In accordance with this interaction, a directly proportional relationship was derived between FS and the intrinsic gas phase molecular volume, V_(int), of the nitramines mentioned, which is divided also into several straight lines according to relatively tight molecular structure similarity. The relationships found again confirm a level of disorder in the distribution of the forces in the crystal lattice of the "common" quality of ε-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane, in comparison with its reduced sensitivity(RS) or chemically pure analogue.

Crystal lattice free volume and thermal decomposition of nitramines

The linear, directly proportional, equations between the Arrhenius parameters(E_α, and log A) of the thermal decomposition and the crystal lattice free space per molecule, △V, of 22 nitramines are described. It is shown that, because of a significant limitation by the molecular structural characteristics of such compounds, they are divided into a number of partial relationships. These partial relationships divide the nitramines into a group of substances relating to dimethyl nitramine and a sub-group related to e-HNIW. These directly proportional equations mean that an increase in the △Vvalues is related to an increase in the thermal stability of the corresponding nitramines. A comparison with similar published dependencies for the impact and friction sensitivities, on the one hand, and with the relationship between the E_a values and the sum of the negative and positive extremes of molecular surface electrostatic potentials, on the other, confirms the well-known fact that intermolecular interaction in the nitramines studied plays a decisive role in the thermal reactivity of such compounds. The crystal lattice free space manifests itself here perhaps only in the solid state thermal decomposition of RDX, HMX and DINGU. This study again confirms a level of disorder in the distribution of the forces in the crystal lattice of the"common" quality of e-HNIW,compared with its "reduced sensitivity(RS)" or pure analogues.

以环状硝胺为基的几种塑料黏结炸药的初步研究(英文)

用聚异丁烯(PIB),丙烯腈-聚丁橡胶(ABR),维通A黏结剂和RDX,HMX,BCHMX和ε-HNIW四种硝胺炸药制备了一系列塑性炸药。PETN和以PETN为基的三种塑性炸药用于比较。测试了这些炸药的爆速,撞击和摩擦感度。摩擦感度与撞击感度的关系以及两种感度与D2的关系表明摩擦力向硝胺炸药分子反应中心的转移机理不同于撞击能的转移机理。从摩擦和撞击反应的相互比较以及降低ε-HNIW感度等级中发现撞击感度依赖于硝铵炸药的晶体品质,而摩擦感度的依赖却不明显。测试爆速D与含PIB和ABR黏结剂的PBX装药密度之间的关系表明,ε-HNIW的密度为2.04 g·cm-3时,爆速D为9.800 mm·μs-1。

Impact Sensitivity in Respect of the Crystal Lattice Free Volume and the Characteristics of Plasticity of Some Nitramine Explosives

The relationship between the crystal lattice free volume,ΔV,and impact sensitivity,E_(dr),of ten nitramines has been analyzed. It was found that this relationship is not uniquely determined,i. e. it is not given only by their own ΔV values but fundamentally by the type and intensity of the intermolecular forces in the nitramine crystals. Also,relationships between the E_(dr)values,on the one hand,and bulk modulus,K,and shear modulus,G,on the other,have been the subject of discussion not only for pure cyclic nitramines but also for their PBXs,bonded by a poly-fluoro binder. The closest linear correlation exists between the E_(dr)values and dimensionless K·G^(-1) ratio which indicates the plasticity range. A similar relationship is valid also for the ΔV values. Relationships of the E_(dr) and / or ΔV values with the shear modulus or to the K·G^(-1) ratio reflect an unusual behavior of ε-HNIW to which the published morphological instability of this particular HNIW version might also be related.

Friction Sensitivity of Nitramines. Part Ⅲ:Comparison with Detonation Performance

The friction sensitivities(FS) of five linear and eight cyclic nitramines have been determined.These FS values were compared with the respective detonation velocities,D,and with the dimensionless ratio created by relating the heat of explosion,Qreal,to the activation energy,Ea,of non-autocatalyzed thermal decomposition of the explosives concerned.For the nitramaines studied,these comparisons show a general trend of FS decreasing with increasing energy content.

多硝基芳烃的电火花感度和热安定性关系(英文)

An ESZ KTTV instrument of a new,relatively simple construction has been applied to determination of electric spark sensitivity of 29 polynitro arenes,expressed as spark energy,EES,required for 50-percent initiation probability.The thermal stability thresholds,Tmax,were calculated from the published Arrhenius parameters of monomolecular thermal decomposition of the studied compounds,predominantly obtained under the conditions of the Russian manometric method.An approximate relationship has been found between the ln EES values and threshold Tmax values.In the sense of this relationship,the compounds studied fall into several sub-groups.The reason of the said diversification lies in the decomposition reaction rate at the temperature of onset of their thermal decomposition.It has been found that in each sub-group increasing thermal stability of polynitro arenes is accompanied by increasing electric spark sensitivity of these substances.This fact must be taken into account if we deal with the problem of electric spark energy transfer into the reaction centre of the molecule.

Effect of energy content of the nitraminic plastic bonded explosives on their performance and sensitivity characteristics

Information about the forty nine nitraminic plastic bonded explosives(PBXs)and different nitramines were collected.Fillers of these PBXs are nitramines 1,3,5-trinitro-1,3,5-triazinane(RDX)and β-1,3,5,7-tetranitro-1,3,5-tetrazocane(β-HMX),cis-1,3,4,6-tetranitro-octahydroimidazo-[4,5-d]imidazole(bicyclo-HMX,BCHMX)and e-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(e-HNIW,CL-20)which are bonded by polyfluoro-elastomers,polydimethyl-siloxane,poly-glycidyl azide,polyisobutylene,polystyrene-butadiene,poly-acrylonitrile-butadiene and hydroxyl-terminated polybutadiene in addition to a melt cast compositions based on 2,4,6-trinitrotoluene.For thirty two of these PBXs the relationships are specified and analyzed between heats of their combustion and relative explosive strengths;by means of these relationships it might be possible to estimate,which groupings in the macromolecule of binder could be liable to their primary fission in the PBXs initiation.Similarly,for forty two of these explosives,the relationships are described and analyzed between their enthalpies of formation and impact sensitivities;here is especially attention paid to PBXs filled by BCHMX.Specific rate constants from Vacuum Stability Test(VST)of four nitramines and twenty PBXs are introduced into relationships with their enthalpies of formation.Regarding to all the mentioned cases,increasing of energy content of the studied explosives leads to increase of the relative explosive strength or initiation reactivity,respectively.Exception with the opposite trend,the outputs of VST are for BCHMX,where in PBXs are matrices with the esteric plasticizers or the energetic poly-glycidyl azide.Admixture of RDX or HMX,respectively,into the BCHX PBXs gives ternary PBXs whose thermal stability,in the sense of applied VST,is higher comparing to the original binary explosives.

Friction Sensitivity of Nitramines. Part Ⅱ:Comparison with Thermal Reactivity

The friction sensitivity(FS) of five linear and eight cyclic nitramines has been determined.Arrhenius parameters of non-autocatalyzed thermal decomposition of these nitramines were used for comparison of the FS values with thermal reactivity.Generally,increasing values of activation energies of non-autocatalyzed decomposition of the studied nitramines are connected with decreasing FS values.A similar trend was found in the relation between FS and hypothetical initiation temperature for 5% conversion of the nitramines after 50 μs of their thermolysis,however,if in the given series of nitramines their initiation reactivity is predominantly determined by the energy content of their molecules and closer similarity of their molecular structures,then the above-mentioned trend may be opposite.The found relationships were used for prediction and verification of the activation energy of non-autocatalyzed thermal decomposition of 2,5-dinitro-2,5-diazahexane.

cis-1,3,4,6-Tetranitrooctahydroimidazo-[4,5-d]imidazole(BCHMX)as a part of explosive mixtures

cis-1,3,4,6-Tetranitrooctahydroimidazo-[4,5-d]imidazole(BCHMX) is a relatively available bicyclic nitramine in the present. Due to the high energetic content of its molecule(deformation of valence angles) it has heat of formation higher than β-1,3,5,7-tetranitro-1,3,5,7-tetrazocane(β-HMX) by nearly three times. As a result, it has heat of explosion and relative explosive strength exceed that of β-HMX including their corresponding PBXs. However, penetration abilities of PBXs based on HMX are higher than those based on BCHMX. The relatively high initiation reactivity of BCHMX could be modified in a wide range by its incorporation in a suitable polymeric matrices. Regarding to the performance, coating of BCHMX crystals by 5 wt% Viton A produces the maximum performance while the mixture of BCHMX with polydimethylsiloxane(PDMS) seems to be the optimum composition for the development of PBX with low sensitivity.

Enhancing the explosive characteristics of a Semtex explosive by involving admixtures of BCHMX and HMX

A well-known ternary plastic explosive,Czech Semtex 1H,contains a mixture of PETN and RDX softened by SBR.In this work,BCHMX was used to replace PETN in Semtex 1H to form Sem-BC+RDX.In addition,another mixture based on BCHMX and HMX as energetic fillers bonded by the polymeric matrix of Semtex 1H(Sem-BC+HMX)was studied.The particle size distribution of each individual explosive was determined to obtain the optimum mixing conditions.Friction and impact sensitivities were determined.The velocity of detonation was reported practically and the detonation properties were calculated by EXPLO5 code.The explosive strength of each sample was measured by the ballistic mortar test.The conclusion confirms that the velocity of detonation of Sem-BC+HMX was the highest in comparison with the prepared samples.Sem-BC+RDX has the least impact and frictions sensitivities.Sem-BC+RDX has higher detonation velocity,detonation properties and explosive strength than Semtex 1H.Addition of BCHMX in Semtex 1H as a replacement for PETN is the candidate to produce a high performance advanced Czech plastic explosive.

Friction Sensitivity of Nitramines. Part Ⅳ:Links to Surface Electrostatic Potentials

The friction sensitivity(FS) of five aliphatic linear and eight cyclic nitramines has been determined and correlated with DFT B3LYP/6-31-G(d,p) // 6-311+G(d,p) positive(VS,max) and negative(VS,min) extremes of molecular surface electrostatic potentials VS(r).While there is an ambiguous relationship between the VS,max values and FS values,the decrease of FS is connected(more or less) with increase in VS,min values.

Comparison with Molecular Surface Electrostatic Potential and Thermal Reactivity of Nitramines

Molecular surface electrostatic potentials V_S(r) ( ESP) of seventeen nitramines have been calculated. As a criterion of the imbalance between the maximum positive,V_(S,max) and minimum negative,V_(S,min),values of molecular surface electrostatic potentials their sum was derived and used as a new simple characteristic for ESPs-V_(S,Σ). These V_(S,Σ) values have close relationships with the Arrhenius parameters,activation energy E_a and preexponent log A,of thermal decomposition of the nitramines studied. The correlation between the V_(S,Σ) values and heats of fusion of the nitramines studied is described. These findings suggested analyzing the physico-chemical behavior of the nitramine crystals during this decomposition; in this connection an investigation was carried out using isothermal thermogravimetry and scanning electron microscopy of thermally exposed crystals of cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole( sintering of its crystal surfaces),of β-1,3,5,7-tetranitro-1,3,5,7-tetrazocane( cracking of its crystals during β !δ transition) and of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane. The results suggest a need to study the pre-decomposition states on thermal decomposition of the nitramines' molecule's crystals.

The role of crystal lattice free volume in nitramine detonation

Crystal lattice free volumes,△V,of 22 nitramines introduced into relationships of maximal theoretical crystal densities(TMD),detonation velocities(D)and volume heats of explosives(ρ.Q).Values of all these characteristics increase with an increase in the AV values.However,more realistic dependencies for the TMD and D values are obtained by using correlations with ratio of the intrinsic molecular volume,Vint,to△V(i.e.Vint/△V),whereby the dependence on the D values reflects their similar relationship to a sum of the positive(VS,max)and negative(VS,min)extremes of the molecular surface electrostatic potentials(VS,∑).Also,directly proportional linear relationships are specified between the VS,∑ values on the one hand,and the △V and Vint/△V values,on the other.It is stated that the crystal lattice free volumes might have a similar role in detonation of nitramines as the intermolecular force effect in their molecular crystals(they are as if representative of such forces).

A new look on the electric spark sensitivity of nitramines

Electric spark energy,E_(ES),for a 50%probability of initiation of the 14 nitramines was determined using a measuring instrument in which the electrodes are in direct contact with the sample.Indirectly proportional relationships were established between the logarithm of the E_(ES)values and the length of the longest N-N bond in the nitramine molecule.This finding is compatible with the mechanism of the first step in the electro-reduction of the nitramine grouping.Directly proportional relationships were found to exist between the E_(ES)values and the crystal lattice free volumes,ΔV(i.e.an increase in theΔV values increases the nitramine's resistance to electric sparks)but there were several nitramines with the opposite course of this relationship.Also a semilogarithic relationships between the E_(ES)values and a ratio of intrinsic volumes of molecule,V_(int),to theΔV values were described as well as ambiguous linear dependence between these energies and a sum of the positive and negative extremes of the molecular surface electrostatic potentials,V_(S,∑).Several nitramines studied(always the same ones)display roughly the same distribution in the coordinate systems of relationships with lengths of the longest N-N bonds,the Vint/ΔV ratio and the sum V_(S,∑)as the independent variables.It was found that,typically,such relationships start from a single identical point,in effect a point corresponding to data for a structural unit from which tho studied nitramines can be hypothetically generated,and/or are converging on another point,often the one corresponding to the data for HNIW.All the findings point to a fundamental influence of the intermolecular forces on reactivity of nitramines exposed to electric sparks.

Relative Explosive Strength of Some Explosive Mixtures Containing Urea and/or Peroxides

Several mixtures,based on urea derivatives and some inorganic oxidants,including also alumina,were studied by means of ballistic mortar techniques with TNT as the reference standard.The detonation pressure(P),detonation velocity(D),detonation energy(Q),and volume of gaseous product at standard temperature and pressure(STP),V,were calculated using EXPLO5V6.3 thermochemical code.The performance of the mixtures studied was discussed in relation to their thermal reactivity,determined by means of differential thermal analysis(DTA).It is shown that the presence of hydrogen peroxide in the form of its complex with urea(i.e.as UHP)has a positive influence on the explosive strength of the corresponding mixtures which is linked to the hydroxy-radical formation in the mixtures during their initiation reaction.These radicals might initiate(at least partially)powdered aluminum into oxidation in the CJ plane of the detonation wave.Mixtures containing UHP and magnesium are dangerous because of potential auto-ignition.