scholarly journals Comparative Theoretical Studies on a Series of Novel Energetic Salts Composed of 4,8-Dihydrodifurazano[3,4-b,e]pyrazine-based Anions and Ammonium-based Cations

Molecules ◽  
2019 ◽  
Vol 24 (18) ◽  
pp. 3213 ◽  
Author(s):  
Binghui Duan ◽  
Ning Liu ◽  
Bozhou Wang ◽  
Xianming Lu ◽  
Hongchang Mo
Keyword(s):  
High Performance ◽  
Density Functional ◽  
Parent Compound ◽  
Impact Sensitivity ◽  
Detonation Performance ◽  
Heats Of Formation ◽  
Detonation Properties ◽  
Detonation Pressure ◽  
Derivative Work ◽  
Energetic Salts

4,8-Dihydrodifurazano[3,4-b,e]pyrazine (DFP) is one kind of parent compound for the synthesis of various promising difurazanopyrazine derivatives. In this paper, eleven series of energetic salts composed of 4,8-dihydrodifurazano[3,4-b,e]pyrazine-based anions and ammonium-based cations were designed. Their densities, heats of formation, energetic properties, impact sensitivity, and thermodynamics of formation were studied and compared based on density functional theory and volume-based thermodynamics method. Results show that ammonium and hydroxylammonium salts exhibit higher densities and more excellent detonation performance than guanidinium and triaminoguanidinium salts. Therein, the substitution with electron-withdrawing groups (–NO2, –CH2NF2, –CH2ONO2, –C(NO2)3, –CH2N3) contributes to enhancing the densities, heats of formation, and detonation properties of the title salts, and the substitution of –C(NO2)3 features the best performance. Incorporating N–O oxidation bond to difurazano[3,4-b,e]pyrazine anion gives a rise to the detonation performance of the title salts, while increasing their impact sensitivity meanwhile. Importantly, triaminoguanidinium 4,8-dihydrodifurazano[3,4-b,e]pyrazine (J4) has been successfully synthesized. The experimentally determined density and H50 value of J4 are 1.602 g/cm3 and higher than 112 cm, which are consistent with theoretical values, supporting the reliability of calculation methods. J4 proves to be a thermally stable and energetic explosive with decomposition peak temperature of 216.7 °C, detonation velocity 7732 m/s, and detonation pressure 25.42 GPa, respectively. These results confirm that the derivative work in furazanopyrazine compounds is an effective strategy to design and screen out potential candidates for high-performance energetic salts.

scholarly journals Design and Selection of Pyrazolo[3,4-d][1,2,3] Triazole-based High-energy Materials

2021 ◽  
Author(s):  
Xinghui Jin ◽  
Luhao Liu ◽  
Jianhua Zhou ◽  
Bingcheng Hu
Keyword(s):  
Electronic Structures ◽  
Density Functional ◽  
High Energy ◽  
Impact Sensitivity ◽  
High Energy Density ◽  
Heats Of Formation ◽  
Detonation Properties ◽  
Detonation Pressure ◽  
The Impact ◽  
Impact Sensitivities

Abstract In this study, we design a series of bridged energetic compounds based on pyrazolo[3,4-d][1, 2, 3]triazole to screen potential energetic materials with excellent detonation properties and acceptable sensitivities. The electronic structures, heats of formation, detonation velocity, detonation pressure, and impact sensitivity of the designed compounds were calculated using density functional theory. The results showed that the designed compounds have high positive heats of formation in the range of 1035.4 (A7) to 2851.4 kJ mol−1 (D2). Moreover, the designed compounds have high crystal densities and heats of detonation, which significantly enhance detonation pressures and velocities. The detonation pressures and velocities are in the ranges of 6.23 (A1) to 9.65 km s−1 (D3) and 15.7 to 43.9 GPa (E8), respectively. The impact sensitivity data also suggest that the designed compounds have impact sensitivities in an acceptable range. Considering detonation pressures, detonation velocities, and impact sensitivities, six compounds (C3, C5, D3, D5, E3, and F3) were screened as potential materials with high energy density, excellent detonation properties, and low impact sensitivities. Finally, the electronic structures of the screened compounds were simulated to provide further understanding on the physicochemical properties of these compounds.

Molecular design on a new family of azaoxaadamantane cage compounds as potential high-energy density compounds

2019 ◽  
Vol 97 (2) ◽  
pp. 86-93 ◽  
Author(s):  
Yong Pan ◽  
Weihua Zhu ◽  
Heming Xiao
Keyword(s):  
Thermal Stability ◽  
Density Functional ◽  
Parent Compound ◽  
High Energy ◽  
High Energy Density ◽  
Lower Sensitivity ◽  
Detonation Properties ◽  
Detonation Pressure ◽  
Cage Compounds ◽  
New Family

A new family of azaoxaadamantane cage compounds were firstly designed by introducing the oxygen atom into hexanitrohexaazaoxaadmantane (HNHAA) to replace the N–NO2 group. Their properties including heats of formation (HOFs), detonation properties, strain energies, thermal stability, and sensitivity were extensively studied by using density functional theory. All of the title compounds exhibit surprisingly high density (ρ > 2.01 g/cm3) and excellent detonation properties (detonation velocity (D) > 9.29 km/s and detonation pressure (P) > 40.80 GPa). In particular, B (4,8,9,10-tetraazadioxaadamantane) and C (6,8,9,10-tetraazadioxaadamantane) have a remarkably high D and P values (9.70 km/s and 44.45 GPa, respectively), which are higher than that of HNHAA or CL-20. All of the title compound have higher thermal stability and lower sensitivity (h50 > 19.58 cm) compared with the parent compound HNHAA. Three triazatrioxaadamantane cage compounds, D (6,8,9-triazatrioxaadamantane), E (6,8,10-triazatrioxaadamantane), and F (8,9,10-triazatrioxaadamantane), are expected to be relatively insensitive explosives. All of the title compounds exhibit a combination of high denotation properties, good thermal stability, and low insensitivity.

Density functional study of guanidine-azole salts as energetic materials

2018 ◽  
Vol 96 (10) ◽  
pp. 949-956 ◽  
Author(s):  
Si-Yu Xu ◽  
Zhou-Yu Meng ◽  
Feng-Qi Zhao ◽  
Xue-Hai Ju
Keyword(s):  
Energetic Materials ◽  
Density Functional ◽  
Dft Method ◽  
Impact Sensitivity ◽  
Detonation Performance ◽  
Functional Study ◽  
Detonation Properties ◽  
Geometrical Structures ◽  
Counter Ions ◽  
The Density Functional Theory

A series of guanidine cations and azole anions were designed for use as energetic salts. Their geometrical structures were optimized by the density functional theory (DFT) method. The counter ions were matched by the similar magnitude of the electron affinity (EA) of the cation and the ionization potential (IP) of the anion. The densities, heats of formation, detonation parameters, and impact sensitivity were predicted. The incorporation of guanidine cations and diazole anions are favorable to form thermal stable salts except cation A1. The diaminoguanidine cation has greater impact on the density and detonation properties of the salts than the triaminoguanidine cation. 2-Amino-3-nitroamino-4,5-nitro-dinitropyrazole is the best anion for advancing the detonation performance among all the anions. Incorporating the C=O bond into the guanidine cations enhances the density and detonation performance of the guanidine-azole salts. The salts containing III1–III4 anion have better detonation properties than HMX, indicating that these salts are potential energetic compounds. Compared with RDX or HMX, some salts with diaminoguanidine cation display lower impact sensitivity.

Comparative theoretical studies of dinitromethyl- or trinitromethyl-modified derivatives of CL-20

2013 ◽  
Vol 91 (12) ◽  
pp. 1243-1251 ◽  
Author(s):  
Yong Pan ◽  
Weihua Zhu ◽  
Heming Xiao
Keyword(s):  
Thermal Stability ◽  
Density Functional ◽  
Parent Compound ◽  
Initial Step ◽  
Impact Sensitivity ◽  
Detonation Properties ◽  
Energetic Properties ◽  
The Stability ◽  
The Impact ◽  
Trinitromethyl Group

The heats of formation (HOFs), energetic properties, strain energies, thermal stability, and impact sensitivity for a series of trinitromethyl- or dinitromethyl-modified CL-20 derivatives were studied by using density functional theory. It is found that the trinitromethyl group is an effective structural unit for improving the gas-phase HOFs and energetic properties of the derivatives. However, incorporating the dinitromethyl group into the parent compound is not favorable for increasing its HOFs and detonation properties. The effects of the dinitromethyl or trinitromethyl groups on the stability of the parent compound are discussed. The studies on strain energies show that the introduction of the trinitromethyl group intensifies the strain of the cage skeleton for the title compounds, whereas for the dinitromethyl groups, the case is quite the contrary. An analysis of the bond dissociation energies for several relatively weak bonds suggests that the substitution of the dinitromethyl or trinitromethyl group decreases the thermal stability of the derivatives. The C−NO2 bond in the dinitromethyl or trinitromethyl group is the weakest one and the homolysis of the C−NO2 bond may be the initial step in thermal decomposition. In addition, according to the calculated free space per molecule, the introduction of the dinitromethyl or trinitromethyl group increases the impact sensitivities of the derivatives. Considering the detonation performance, thermal stability, and impact sensitivity, six compounds can be regarded as the target high-energetic compounds.

EMPIRICAL METHODS FOR ESTIMATING THE DETONATION PROPERTIES OF ENERGETIC TNAZ MOLECULAR DERIVATIVES

2004 ◽  
Vol 03 (03) ◽  
pp. 379-389 ◽  
Author(s):  
MIN-HSIEN LIU ◽  
CHENG CHEN ◽  
YAW-SHUN HONG
Keyword(s):  
Density Functional ◽  
Dft Calculation ◽  
Enthalpies Of Formation ◽  
Detonation Properties ◽  
Group Additivity ◽  
Detonation Pressure ◽  
Empirical Methods ◽  
Functional Theory ◽  
Simulation Results ◽  
Hybrid Density Functional

Following the successful synthesis of the TNAZ (1,3,3-trinitroazetidine), the amine reactant is theoretically replaced to yield the hypothesized TNAZ molecular derivatives. Hybrid density-functional theory (DFT) calculation method was applied to model TNAZ and its derivatives. In this investigation, the target molecular volumes were initially obtained using the group additivity approach, and then transferred into molecular densities. The densities and the least squares estimated enthalpies of formation (ΔHf) of TNAZ, and the corresponding derivatives, were obtained and the Kamlet–Jacobs empirical equations were used to determine the related detonation velocity and detonation pressure. The simulation results reveal that four of the TNAZ molecular derivatives perform similarly to the traditionally used RDX (1,3,5-trinitro-1,3,5-triazacyclohexane). Two other derivatives outperform RDX, with performance that approach that of HMX (1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane).

Searching for a new family of high energy explosives by introducing N atoms, N-oxides, and NO2 into a cage adamantane

2016 ◽  
Vol 94 (8) ◽  
pp. 667-673 ◽  
Author(s):  
Dong Xiang ◽  
Hao Chen ◽  
Weihua Zhu ◽  
Heming Xiao
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Design Strategy ◽  
High Energy ◽  
Impact Sensitivity ◽  
Lower Sensitivity ◽  
Detonation Properties ◽  
Potential Candidate ◽  
Functional Theory ◽  
New Family

A design strategy that including N atoms, N-oxides, and nitro groups into a cage azaadamantane at the same time was used to design 10 polyazaoxyadamantanes (PAOAs) and eight polynitroazaoxyadamantanes (PNTAOAs). First, four stable azaadamantanes were built by replacing the tertiary C atoms of an adamantane with N atoms. Then, 10 PAOAs were designed by introducing one to four N-oxides into the four azaadamantanes. After that, eight PNTAOAs were formed when the H atoms of four N-oxide-substituted azaadamantanes were replaced with different numbers of nitro groups. Finally, their heats of formation, densities, detonation properties, and impact sensitivity were estimated by using density functional theory. Among the eight PNTAOAs, seven compounds had better detonation performances than CL-20, the outstanding, novel, high-energy, and relatively insensitive cage explosive. Two compounds had higher detonation performance and lower sensitivity than CL-20 and HMX, suggesting that their overall performances are outstanding and they may be considered as the potential candidate of high-energy explosives.

scholarly journals Theoretical studies of novel high energy density materials based on oxadiazoles

2021 ◽  
Author(s):  
Wenxin Xia ◽  
Renfa Zhang ◽  
Xiaosong Xu ◽  
Congming Ma ◽  
Peng Ma ◽  
...  
Keyword(s):  
Density Functional ◽  
High Energy ◽  
Heat Of Formation ◽  
High Energy Density ◽  
Detonation Properties ◽  
Detonation Pressure ◽  
Energetic Compounds ◽  
Functional Theory ◽  
High Energy Density Materials ◽  
Thermal Stability Of

Abstract In this study, 32 energetic compounds were designed using oxadiazoles (1,2,5-oxadiazole, 1,3,4-oxadiazole) as the parent by inserting different groups as well as changing the bridge between the parent. These compounds had high-density and excellent detonation properties. The electrostatic potentials of the designed compounds were analyzed using density functional theory (DFT). The structure, heat of formation (HOF), density, detonation performances (detonation pressure P , detonation velocity D , detonation heat Q ), and thermal stability of each compound were systematically studied based on molecular dynamics. The results showed that the -N 3 group has the greatest improvement in HOF. For the detonation performances, the directly linked, -N=N-, -NH-NH- were beneficial when used as a bridge between 1,2,5-oxadiazole and 1,3,4-oxadiazole, and it can also be found that bridge changing had little effect on the trend of detonation performance, while energetic groups changing influenced differently. The designed compounds (except for A2 , B2 , B4 ) all had higher detonation properties than TNT, A6 ( D = 9.41 km s -1 , P = 41.86 GPa, Q = 1572.251 cal g -1 ) was the highest, followed D6 had poorer performance ( D = 8.96 km s -1 , P = 37.46 GPa, Q = 1354.51 cal g -1 ).

Molecular design of N–NO2substituted cycloalkanes derivatives Cm(N–NO2)mfor energetic materials with high detonation performance and low impact sensitivity

RSC Advances ◽  
2015 ◽  
Vol 5 (48) ◽  
pp. 38048-38055 ◽  
Author(s):  
Yan-Yan Guo ◽  
Wei-Jie Chi ◽  
Ze-Sheng Li ◽  
Quan-Song Li
Keyword(s):  
Energetic Materials ◽  
Molecular Design ◽  
Impact Sensitivity ◽  
Detonation Performance ◽  
Detonation Properties

Cycloalkane derivatives Cm(N–NO2)mexhibit notable detonation properties and remarkable stability for potential energetic materials.

Theoretical study of energetic carbon-oxidized triazole and tetrazole derivatives

2015 ◽  
Vol 93 (3) ◽  
pp. 368-374 ◽  
Author(s):  
Guolin Xiong ◽  
Zhichao Liu ◽  
Qiong Wu ◽  
Weihua Zhu ◽  
Heming Xiao
Keyword(s):  
Thermal Stability ◽  
Density Functional ◽  
Theoretical Study ◽  
Molecular Design ◽  
High Energy ◽  
Heat Of Formation ◽  
Detonation Performance ◽  
Detonation Properties ◽  
Functional Theory ◽  
Tetrazole Derivatives

We investigated the heat of formation, density, thermal stability, and detonation properties of a series of carbon-oxidized triazole and tetrazole derivatives substituted by –NH2 and –NO2 groups using density functional theory. It is found that their properties are associated with the numbers of substituents and substitution positions in the parent ring. The results show that the –NO2 group is an effective structural unit for enhancing their detonation performance. It also indicates that the substitution positions play a very important role in increasing the heat of formation values of the derivatives. An analysis of impact sensitivity (h50) indicates that incorporating the –NH2 groups into the parent ring increases their thermal stability. Considering the detonation performance and thermal stability, seven of the designed compounds may be regarded as potential high-energy compounds. These results provide basic information for the molecular design of novel high-energy compounds.

scholarly journals Screening for energetic compounds based on 1,3-dinitrohexahydropyrimidine skeleton and 5-various explosopheres: molecular design and computational study

2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Binghui Duan ◽  
Ning Liu ◽  
Xianming Lu ◽  
Hongchang Mo ◽  
Qian Zhang ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Energetic Materials ◽  
Molecular Design ◽  
Computational Study ◽  
Impact Sensitivity ◽  
Detonation Properties ◽  
Detonation Pressure ◽  
Energetic Compounds ◽  
Good Thermal Stability ◽  
Energetic Performance

Abstract In this paper, twelve 1,3-dinitrohexahydropyrimidine-based energetic compounds were designed by introducing various explosopheres into hexahydropyrimidine skeleton. Their geometric and electronic structures, heats of formation (HOFs), energetic performance, thermal stability and impact sensitivity were discussed. It is found that the incorporation of electron-withdrawing groups (–NO2, –NHNO2, –N3, –CH(NO2)2, –CF(NO2)2, –C(NO2)3) improves HOFs of the derivatives and all the substituents contribute to enhancing the densities and detonation properties (D, P) of the title compounds. Therein, the substitution of –C(NO2)3 features the best energetic performance with detonation velocity of 9.40 km s−1 and detonation pressure of 40.20 GPa. An analysis of the bond dissociation energies suggests that N–NO2 bond may be the initial site in the thermal decompositions for most of the derivatives. Besides, –ONO2 and –NF2 derivatives stand out with lower impact sensitivity. Characters with striking detonation properties (D = 8.62 km s−1, P = 35.08 GPa; D = 8.81 km s−1, P = 34.88 GPa), good thermal stability, and acceptable impact sensitivity (characteristic height H50 over 34 cm) lead novel compounds 5,5-difluoramine-1,3-dinitrohexahydropyrimidine (K) and 5-fluoro-1,3,5-trinitrohexahydropyrimidine (L) to be very promising energetic materials. This work provides the theoretical molecular design and a reasonable synthetic route of L for further experimental synthesis and testing.

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