Accelerating the discovery of insensitive high-energy-density materials by a materials genome approach

Nature Communications, Journal Year: 2018, Volume and Issue: 9(1)

Published: June 18, 2018

Finding new high-energy-density materials with desired properties has been intensely-pursued in recent decades. However, the contradictory relationship between high energy and low mechanical sensitivity makes innovation of insensitive an enormous challenge. Here, we show how a genome approach can be used to accelerate discovery high-energy explosives by identification "genetic" features, rapid molecular design, screening, as well experimental synthesis target molecule, 2,4,6-triamino-5-nitropyrimidine-1,3-dioxide. This as-synthesized energetic compound exhibits graphite-like layered crystal structure measured density 1.95 g cm-3, thermal decomposition temperature 284 °C, detonation velocity 9169 m s-1, extremely sensitivities (impact sensitivity, >60 J friction >360 N). Besides considered system six-member aromatic hetero-aromatic rings, this also applicable development high-performing materials.

Language: Английский

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Synthesis and Characterization of cyclo-Pentazolate Salts of NH₄⁺, NH₃OH⁺, N₂H₅⁺, C(NH₂)₃⁺, and N(CH₃)₄⁺

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(48), P. 16488 - 16494

Published: Nov. 5, 2018

A breakthrough in polynitrogen chemistry was recently achieved by our bulk synthesis of (N5)6(H3O)3(NH4)4Cl which the cyclo-pentazolate anions were stabilized extensively hydrogen bridges with NH4+ and OH3+ cations. Significant efforts have been carried out to replace these nonenergetic cations Cl– anion more energetic In this paper, metathetical syntheses salts containing simple nitrogen-rich NH4+, NH3OH+, N2H5+, C(NH2)3+, N(CH3)4+ are reported. These characterized their crystal structures; vibrational, mass, multinuclear NMR spectra; thermal stability measurements; sensitivity data; performance calculations. It is shown that cyclo-pentazolates than corresponding azides but thermally less stable decomposing range 80 °C 105 °C. As explosives, hydrazinium hydroxyl ammonium predicted match detonation pressure RDX exhibit significantly higher velocities HMX comparable impact friction sensitivities. Although salt has a lower RDX, its velocity also exceeds those HMX. rocket propellant, exceed performances The structures show generally bonds cations, except for exhibits strong cation-π interactions. This difference stabilization detectable vibrational spectra decrease cyclo-N5− stretching vibrations about 20 cm–1.

Language: Английский

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Bipyrazole bearing ten nitro groups – a novel highly dense oxidizer for forward-looking rocket propulsions

Journal of Materials Chemistry A, Journal Year: 2018, Volume and Issue: 6(30), P. 14780 - 14786

Published: Jan. 1, 2018

Novel high-density oxidizer based on highly nitrated bipyrazole was developed. It is the champion among heteroaromatic CHNO compounds with a density equal to 2.021 g cm⁻³ at room temperature.

Language: Английский

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Bis(3-nitro-1-(trinitromethyl)-1H-1,2,4-triazol-5-yl)methanone: An Applicable and Very Dense Green Oxidizer

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(50), P. 19581 - 19584

Published: Nov. 28, 2019

Ammonium perchlorate (AP) is most often used as a practical solid rocket propellant because of its excellent performance. However, AP has many shortcomings, including instability, high negative enthalpy formation, and claimed health environmental issues resulting from combustion products. The pursuit highly dense, high-performance, environmentally friendly oxidizers propellants long attracted scientists around the world. In this work, bis(3-nitro-1-(trinitromethyl)-1H-1,2,4-triazol-5-yl)methanone (3) was obtained bis(3-nitro-1H-1,2,4-triazol-5-yl)methane (1) with chloroacetone followed by nitration. structure 3 confirmed elemental analysis single-crystal X-ray diffraction. By introducing carbonyl moiety, density increased to 1.945 g/cm3 decomposition temperature 164 °C. Compound green energetic oxidizer that positive oxygen balance (+8.7%), specific impulse (218 s), an acceptable sensitivity (9 J, 240 N), making it replacement for in formulations.

Language: Английский

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Hunting for advanced high-energy-density materials with well-balanced energy and safety through an energetic host–guest inclusion strategy

Journal of Materials Chemistry A, Journal Year: 2019, Volume and Issue: 7(33), P. 19248 - 19257

Published: Jan. 1, 2019

A versatile host–guest driven explosive-oxidant inclusion strategy was proposed to develop advanced high-energy-density materials (HEDMs) with high detonation performances, low mechanical sensitivities and excellent combustion properties.

Language: Английский

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Metal-Free Molecular Perovskite High-Energetic Materials

Crystal Growth & Design, Journal Year: 2020, Volume and Issue: 20(3), P. 1891 - 1897

Published: Feb. 12, 2020

Metal-free energetic materials generally have the advantages of high gas yield and metal-free residue after combustion or explosion, enabling them to be widely used as explosives propellant components. As part a series our investigations on ABX3 molecular perovskite high-energetic materials, here we report five new members, (H2A)[NH4(ClO4)3], by using different organic cations H2A2+, i.e., 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium for DAP-O4, piperazine-1,4-diium PAP-4, 1-methyl-piperazine-1,4-diium PAP-M4, homopiperazine-1,4-diium PAP-H4, 1-methyl-1,4-diazabicyclo-[2.2.2]octane-1,4-diium DAP-M4, respectively. Together with previously reported member, (H2dabco)[NH4(ClO4)3] (DAP-4, H2dabco2+ = 1,4-diazabicyclo[2.2.2]octane-1,4-diium), these six provide nice instances fine-tune oxygen balance, crystal density, thermal stability, detonation performance, changing A-site solely. The density functional theory (DFT) calculations Kamlet–Jacob (K–J) equation suggested that improving balance while keeping spherical shape match anionic cage in facilitates obtaining better providing an important clue designing advanced practicable materials. It is worth noting three compounds (PAP-4, DAP-O4) are expected exceed performances RDX both explosive propellant, which DAP-O4 has highest heat (6.21 kJ mol–1), velocity (8.900 km s–1), pressure (35.7 GPa), well higher specific impulse value (262 s).

Language: Английский

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Construction of an Unusual Two-Dimensional Layered Structure for Fused-Ring Energetic Materials with High Energy and Good Stability

Engineering, Journal Year: 2020, Volume and Issue: 6(9), P. 1006 - 1012

Published: June 10, 2020

The creation of high-performance energetic materials with good mechanical sensitivities has been a great challenge over the past decades, since such have huge amounts energy and are thus essentially unstable. Here, we report on promising fused-ring material an unusual two-dimensional (2D) structure, 4-nitro-7-azido-pyrazol-[3,4-d]-1,2,3-triazine-2-oxide (NAPTO), whose unique 2D structure confirmed by single-crystal X-ray diffraction. Experimental studies show that this novel compound remarkably high (detonation velocity D = 9.12 km·s−1; detonation pressure P 35.1 GPa), excellent toward external stimuli (impact sensitivity IS 18 J; friction FS 325 N; electrostatic discharge EDS 0.32 J) thermal decomposition temperature (203.2 °C), possessing dual advantages low sensitivities. To our knowledge, NAPTO is first layered crystal stacking. stabilization mechanism were investigated using molecular simulations, theoretical calculation results demonstrate ultraflat can buffer more effectively than other structures converting acting into layer sliding compression. Our study reveals promise for creating advanced materials.

Language: Английский

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Introduction of energetic bis-1,2,4-triazoles bridges: A strategy towards advanced heat resistant explosives

Chemical Engineering Journal, Journal Year: 2021, Volume and Issue: 429, P. 132416 - 132416

Published: Sept. 13, 2021

Language: Английский

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Promising Thermally Stable Energetic Materials with the Combination of Pyrazole–1,3,4-Oxadiazole and Pyrazole–1,2,4-Triazole Backbones: Facile Synthesis and Energetic Performance

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(44), P. 49898 - 49908

Published: Oct. 26, 2022

Thermally stable energetic materials have broad applications in the deep mining, oil and natural exploration, aerospace industries. The quest for thermally (heat-resistant) with high energy output low sensitivity has fascinated many researchers worldwide. In this study, two different series of salts based on pyrazole–oxadiazole pyrazole–triazole (3–23) explosophoric groups been synthesized a simple straightforward manner. All newly compounds were fully characterized by IR, ESI-MS, multinuclear NMR spectroscopy, elemental analysis, thermogravimetric analysis–differential scanning calorimetry measurements. structures 3, 7, 22 supported single-crystal X-ray diffraction studies. density, heat formation, properties (detonation velocity detonation pressure) all range between 1.75 1.94 g cm–3, 0.73 to 2.44 kJ g–1, 7689 9139 m s–1, 23.3 31.5 GPa, respectively. are insensitive impact (>30 J) friction (>360 N). addition, 4, 6, 10, 14, 17, 21, 22, 23 show onset decomposition temperature (Td 238 397 °C) than benchmark RDX = 210 °C), HMX (279 HNS (318 °C). It is noteworthy that backbones greatly influence their physicochemical properties. Overall, study offers perspective nitrogen-rich explores relationship structure performance.

Language: Английский

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Facile synthesis of nitroamino-1,3,4-oxadiazole with azo linkage: a new family of high-performance and biosafe energetic materials

Journal of Materials Chemistry A, Journal Year: 2022, Volume and Issue: 10(42), P. 22803 - 22811

Published: Jan. 1, 2022

Energetic materials serve as remarkable fuel/propellants for space shuttles, and their utility in civil military applications is vast.

Language: Английский

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