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...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.展开更多
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 mo...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.展开更多
文摘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.
文摘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.
