scholarly journals Energetic Butterfly: Heat-Resistant Diaminodinitro trans-Bimane

Molecules ◽  
2019 ◽  
Vol 24 (23) ◽  
pp. 4324 ◽  
Author(s):  
Zhang ◽  
Kumar ◽  
Zhang ◽  
Shem-Tov ◽  
Petrutik ◽  
...  
Keyword(s):  
Energetic Materials ◽  
Density Functional ◽  
Energetic Material ◽  
Decomposition Temperature ◽  
Unit Cell ◽  
Computational Techniques ◽  
Detonation Pressure ◽  
Design And Synthesis ◽  
Heat Resistant ◽  
Molecular Arrangement

Due to a significant and prolific activity in the field of design and synthesis of new energetic molecules, it becomes increasingly difficult to introduce new explosophore structures with attractive properties. In this work, we synthesized a trans-bimane-based energetic material—3,7-diamino-2,6-dinitro-1H,5H-pyrazolo-[1,2-a]pyrazole-1,5-dione (4), the structure of which was comprehensively analyzed by a variety of advanced spectroscopic methods and by X-ray crystallo-graphy (with density of 1.845 g·cm−3 at 173 K). Although obtained crystals of 4 contained solvent molecules in their structure, state-of-the-art density functional theory (DFT) computational techniques allowed us to predict that solvent-free crystals of this explosive would preserve a similar tightly packed planar layered molecular arrangement, with the same number of molecules of 4 per unit cell, but with a smaller unit cell volume and therefore higher energy density. Explosive 4 was found to be heat resistant, with an onset decomposition temperature of 328.8 °C, and was calculated to exhibit velocity of detonation in a range of 6.88–7.14 km·s−1 and detonation pressure in the range of 19.14–22.04 GPa, using for comparison both HASEM and the EXPLO 5 software. Our results indicate that the trans-bimane explosophore could be a viable platform for the development of new thermostable energetic materials.

scholarly journals Energetic Windmill: Computational insight into planar guanidine-based nitroazole-substituted compounds as energetic materials

2021 ◽  
Author(s):  
Jingru Li ◽  
Zujia Lu ◽  
Bokun Li ◽  
Hao Wu ◽  
Jiaxuan Wu ◽  
...  
Keyword(s):  
Detonation Velocity ◽  
Energetic Materials ◽  
Density Functional ◽  
Energetic Material ◽  
Molecular Surface ◽  
Frontier Molecular Orbital ◽  
Detonation Pressure ◽  
Planar Structures ◽  
New Type ◽  
Thermochemical Parameters

In this work, we designed a series of energetic materials with a windmill-like structure based on guanidine and nitroazole, and optimized them at the B3LYP/6-311G** level using density functional theory (DFT). According to the optimization results, 6 molecules with planar structures were screened out from 28 molecules and their regularities were summarized. We calculated their geometry, natural bond orbital (NBO) charge, frontier molecular orbital, molecular surface electrostatic potential, and thermochemical parameters. In addition, their properties such as density, enthalpy of formation, detonation velocity, detonation pressure and impact sensitivity are also predicted. The result shows that this series of compounds is a promising new type of energetic material, especially compound 1 has superior detonation velocity and detonation pressure (D=9720m/s, P=41.9GPa).

scholarly journals Van der Waals Density Functional Theory vdW-DFq for Semihard Materials

Crystals ◽  
2019 ◽  
Vol 9 (5) ◽  
pp. 243 ◽  
Author(s):  
Qing Peng ◽  
Guangyu Wang ◽  
Gui-Rong Liu ◽  
Suvranu De
Keyword(s):  
Density Functional Theory ◽  
Energetic Materials ◽  
Density Functional ◽  
Energetic Material ◽  
Van Der Waals ◽  
Molecular Crystals ◽  
Soft Materials ◽  
Dispersion Force ◽  
Electronic Charge ◽  
Functional Theory

There are a large number of materials with mild stiffness, which are not as soft as tissues and not as strong as metals. These semihard materials include energetic materials, molecular crystals, layered materials, and van der Waals crystals. The integrity and mechanical stability are mainly determined by the interactions between instantaneously induced dipoles, the so called London dispersion force or van der Waals force. It is challenging to accurately model the structural and mechanical properties of these semihard materials in the frame of density functional theory where the non-local correlation functionals are not well known. Here, we propose a van der Waals density functional named vdW-DFq to accurately model the density and geometry of semihard materials. Using β -cyclotetramethylene tetranitramine as a prototype, we adjust the enhancement factor of the exchange energy functional with generalized gradient approximations. We find this method to be simple and robust over a wide tuning range when calibrating the functional on-demand with experimental data. With a calibrated value q = 1.05 , the proposed vdW-DFq method shows good performance in predicting the geometries of 11 common energetic material molecular crystals and three typical layered van der Waals crystals. This success could be attributed to the similar electronic charge density gradients, suggesting a wide use in modeling semihard materials. This method could be useful in developing non-empirical density functional theories for semihard and soft materials.

New concept for the design of zero-hydrogen energetic materials with high energy and low sensitivity: achieving a good balance among parent compounds, nitro groups, and N-oxides

2017 ◽  
Vol 95 (5) ◽  
pp. 505-511 ◽  
Author(s):  
Qiong Wu ◽  
Linghua Tan ◽  
Zusheng Hang ◽  
Weihua Zhu
Keyword(s):  
Energetic Materials ◽  
Density Functional ◽  
Energetic Material ◽  
Parent Compound ◽  
High Energy ◽  
Design Concept ◽  
New Novel ◽  
Energetic Compound ◽  
The Density Functional Theory ◽  
Low Sensitivity

A new powerful zero-hydrogen energetic compound DNDOBTT (2,7-dinitro-4N,9N-dioxide-bis[1,2,4]-triazolo)[1,5-b:1′,5′e][1,2,4,5] tetrazine) was produced by a new design concept of achieving a balance among the parent compound, nitro groups, and N-oxides. Its structure and properties was studied by the density functional theory. The breaking of N–N bond in the tetrazine ring is an initial decomposition step of DNDOBTT, and the energy barrier was predicted to be 175 kJ·mol−1. DNDOBTT has comparable detonation performance with some CHNO energetic compounds, including the most powerful ONC (octanitrocubane), whereas its sensitivity and thermal stability are obviously lower and better than those of ONC, respectively, indicating that DNDOBTT has both the high energy and reduced sensitivity and may be a valuable candidate for experiments. Therefore, a new novel energetic material DNDOBTT with good overall performance has been obtained successfully by the new design concept, and it may be applied to design and develop other novel improved zero-hydrogen energetic materials.

scholarly journals Nitrated Graphene Oxide Derived from Graphite Oxide: A Promising Energetic Two-Dimensional Material

Nanomaterials ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 58
Author(s):  
Fayang Guan ◽  
Hui Ren ◽  
Lan Yu ◽  
Qingzhong Cui ◽  
Wanjun Zhao ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Graphene Oxide ◽  
Graphite Oxide ◽  
Energetic Materials ◽  
Density Functional ◽  
Electrode Materials ◽  
Energetic Material ◽  
Structure Characterization ◽  
Hydroxyl Groups ◽  
Two Dimensional

In order to synthesize a novel two-dimensional energetic material, nitrated graphene oxide (NGO) was prepared by the nitrification of graphite oxide to make a functional modification. Based on the morphological characterization, the NGO has a greater degree of curl and more wrinkles on the surface. The structure characterization and density functional theory calculation prove that epoxy and hydroxyl groups on the edge of graphite oxide have reacted with nitronium cation (NO2+) to produce nitro and nitrate groups. Hydrophobicity of NGO implied higher stability in storage than graphene oxide. Synchronous simultaneous analysis was used to explore the decomposition mechanism of NGO preliminarily. The decomposition enthalpy of NGO is 662.0 J·g−1 and the activation energy is 166.5 kJ·mol−1. The thermal stability is similar to that of general nitrate energetic materials. The hygroscopicity, thermal stability and flammability of NGO prove that it is a novel two-dimensional material with potential applications as energetic additives in the catalyst, electrode materials and energetic devices.

Design and Synthesis of Two-Dimensional Covalent Organic Frameworks with Four-Arm Cores: Prediction of Remarkable Ambipolar Charge-Transport Properties

2019 ◽  
Author(s):  
Simil Thomas ◽  
Hong Li ◽  
Raghunath R. Dasari ◽  
Austin Evans ◽  
William Dichtel ◽  
...  
Keyword(s):  
Charge Transport ◽  
Organic Semiconductors ◽  
Density Functional ◽  
Polymer Networks ◽  
Two Dimensional ◽  
Covalent Organic Frameworks ◽  
X Ray Diffraction ◽  
Zinc Porphyrin ◽  
Design And Synthesis ◽  
Predicted Values

<p>We have considered three two-dimensional (2D) π-conjugated polymer networks (i.e., covalent organic frameworks, COFs) materials based on pyrene, porphyrin, and zinc-porphyrin cores connected <i>via</i> diacetylenic linkers. Their electronic structures, investigated at the density functional theory global-hybrid level, are indicative of valence and conduction bands that have large widths, ranging between 1 and 2 eV. Using a molecular approach to derive the electronic couplings between adjacent core units and the electron-vibration couplings, the three π-conjugated 2D COFs are predicted to have ambipolar charge-transport characteristics with electron and hole mobilities in the range of 65-95 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup>. Such predicted values rank these 2D COFs among the highest-mobility organic semiconductors. In addition, we have synthesized the zinc-porphyrin based 2D COF and carried out structural characterization via powder X-ray diffraction and surface area analysis, which demonstrates the feasability of these electroactive networks.</p>

Introduction of the acylamino group to bridged bis(nitroamino-1,2,4-triazole): a strategy for tuning the sensitivity of energetic materials

2021 ◽  
Vol 45 (38) ◽  
pp. 18059-18064
Author(s):  
Dongxu Chen ◽  
Jiangshan Zhao ◽  
Hongwei Yang ◽  
Hao Gu ◽  
Guangbin Cheng
Keyword(s):  
Energetic Materials ◽  
Energetic Material

Introduction of the acylamino group into energetic material compounds will contribute to balancing the sensitivity and the energy.

scholarly journals Taming nitroformate through encapsulation with nitrogen-rich hydrogen-bonded organic frameworks

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Jichuan Zhang ◽  
Yongan Feng ◽  
Richard J. Staples ◽  
Jiaheng Zhang ◽  
Jean’ne M. Shreeve
Keyword(s):  
Thermal Stability ◽  
Hydrogen Bonds ◽  
Self Assembly ◽  
Energetic Materials ◽  
Decomposition Temperature ◽  
High Oxygen Content ◽  
The Poor ◽  
Simple Preparation ◽  
First Time ◽  
Hydrogen Bonded

AbstractOwing to its simple preparation and high oxygen content, nitroformate [−C(NO2)3, NF] is an extremely attractive oxidant component for propellants and explosives. However, the poor thermostability of NF-based derivatives has been an unconquerable barrier for more than 150 years, thus hindering its application. In this study, the first example of a nitrogen-rich hydrogen-bonded organic framework (HOF-NF) is designed and constructed through self-assembly in energetic materials, in which NF anions are trapped in pores of the resulting framework via the dual force of ionic and hydrogen bonds from the strengthened framework. These factors lead to the decomposition temperature of the resulting HOF-NF moiety being 200 °C, which exceeds the challenge of thermal stability over 180 °C for the first time among NF-based compounds. A large number of NF-based compounds with high stabilities and excellent properties can be designed and synthesized on the basis of this work.

scholarly journals Comparative thermal research on tetraazapentalene-derived heat-resistant energetic structures

2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Jing Zhou ◽  
Li Ding ◽  
Yong Zhu ◽  
Bozhou Wang ◽  
Xiangzhi Li ◽  
...  
Keyword(s):  
Differential Scanning Calorimetry ◽  
Thermal Decomposition ◽  
Fourier Transform ◽  
Energetic Materials ◽  
Great Influence ◽  
Fourier Transform Infrared ◽  
Thermal Decomposition Mechanism ◽  
Scanning Calorimetry ◽  
In Situ Ftir Spectroscopy ◽  
Heat Resistant

AbstractOrganic inner salt structures are ideal backbones for heat-resistant energetic materials and systematic studies towards the thermal properties of energetic organic inner salt structures are crucial to their applications. Herein, we report a comparative thermal research of two energetic organic inner salts with different tetraazapentalene backbones. Detailed thermal decomposition behaviors and kinetics were investigated through differential scanning calorimetry and thermogravimetric analysis (DSC-TG) methods, showing that the thermal stability of the inner salts is higher than most of the traditional heat-resistant energetic materials. Further studies towards the thermal decomposition mechanism were carried out through condensed-phase thermolysis/Fourier-transform infrared (in-situ FTIR) spectroscopy and the combination of differential scanning calorimetry-thermogravimetry-mass spectrometry-Fourier-transform infrared spectroscopy (DSC-TG-MS-FTIR) techniques. The experiment and calculation results prove that the arrangement of the inner salt backbones has great influence on the thermal decompositions of the corresponding energetic materials. The weak N4-N5 bond in “y-” pattern tetraazapentalene backbone lead to early decomposition process and the “z-” pattern tetraazapentalene backbone exhibits more concentrated decomposition behaviors.

Structure, stability and intramolecular interaction of M(N5)2(M = Mg, Ca, Sr and Ba) : a theoretical study

RSC Advances ◽  
2015 ◽  
Vol 5 (28) ◽  
pp. 21823-21830 ◽  
Author(s):  
Xueli Zhang ◽  
Junqing Yang ◽  
Ming Lu ◽  
Xuedong Gong
Keyword(s):  
Energetic Materials ◽  
Density Functional ◽  
Alkaline Earth ◽  
Theoretical Study ◽  
Intramolecular Interaction ◽  
Earth Metal ◽  
Structure Stability ◽  
Alkaline Earth Metal ◽  
Functional Theory ◽  
The Density Functional Theory

The potential energetic materials, alkaline earth metal complexes of the pentazole anion (M(N5)2, M = Mg2+, Ca2+, Sr2+and Ba2+), were studied using the density functional theory.

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.

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