Development and Evolution of Energetic Cocrystals

Accounts of Chemical Research, Год журнала: 2021, Номер 54(7), С. 1699 - 1710

Опубликована: Март 16, 2021

In spite of the importance energetic materials to a broad range military (munitions, missiles) and civilian (mining, space exploration) technologies, introduction new chemical entities in field occurs at very slow pace. This situation is understandable considering stringent requirements for cost safety that must be met fielded. If existing manufacturing infrastructure could leveraged, then this would offer fundamental shift discovery paradigm. Cocrystallization an approach poised realize goal because it can use make compositions through assembly multiple unique components solid state. account describes early proof-of-principle studies with widely used energetics field, including 2,4,6-trinitrotoluene (TNT) octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), forming cocrystals nonenergetic coformers alter key properties such as density, sensitivity, morphology. The evolution these produce between two detailed, those exploiting intermolecular interaction motifs drive halogen bonding. Implications cocrystallization performance, sensitivity external stimuli, manufacturability are explored each stage. derivation many from common satisfies using already demonstrated cost-effective scale well-understood profiles. concludes discussion cocrystallizing molecules having excess oxidizing power oxygen-deficient push limits explosive performance unprecedented levels. purposeful production arbitrary combination into cocrystal far certain, but described motivate continued exploration novel development predictive models identifying crystallization partners. When form, their most important cannot predicted, pointing another challenge based on cocrystallization.

Язык: Английский

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Luminescent sensing of nitroaromatics by crystalline porous materials

CrystEngComm, Год журнала: 2020, Номер 22(45), С. 7736 - 7781

Опубликована: Янв. 1, 2020

Designing strategies for the syntheses of targeted luminescent MOFs, nanoparticle/MOF composites and COFs described their application in sensing nitroaromatic compounds explosives discussed.

Язык: Английский

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Achieving Balanced Energetics through Cocrystallization

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(48), С. 17185 - 17188

Опубликована: Сен. 23, 2019

Achieving energetic materials with a balanced ratio of oxidant to fuel is challenge that has been difficult meet through molecular synthesis. The alternative approach, composite formulation, fails achieve intimate association the components detriment performance. Herein, oxidizer ammonium dinitramide (ADN) combined fuel-rich pyrazine-1,4-dioxide via cocrystallization. result material oxidant/fuel in which maintain association. exhibits desirable physical and properties are much improved over ADN comparable contemporary energetics.

Язык: Английский

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

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Апрель 9, 2021

Abstract Owing to its simple preparation and high oxygen content, nitroformate [ − C(NO 2 ) 3 , NF] is an extremely attractive oxidant component for propellants explosives. However, the poor thermostability of NF-based derivatives has been unconquerable barrier more than 150 years, thus hindering application. In this study, first example a nitrogen-rich hydrogen-bonded organic framework (HOF-NF) designed constructed through self-assembly in energetic materials, which NF anions are trapped pores resulting via dual force ionic hydrogen bonds from strengthened framework. These factors lead decomposition temperature HOF-NF moiety being 200 °C, exceeds challenge thermal stability over 180 °C time among compounds. A large number compounds with stabilities excellent properties can be synthesized on basis work.

Язык: Английский

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Energetic Derivatives of 8-Nitropyrazolo[1,5-a][1,3,5]triazine-2,4,7-triamine: Achieving Balanced Explosives by Fusing Pyrazole with Triazine

Organic Letters, Год журнала: 2020, Номер 22(4), С. 1321 - 1325

Опубликована: Янв. 30, 2020

Using the triazine ring as stabilizing factor, a series of energy-safety balanced fused compounds were successfully studied. Compounds 1, 7, and 9·H2O further confirmed by single-crystal X-ray diffraction analysis. The detonation performance safety parameters associated with impact friction sensitivities investigated using EXPLO5 (version 6.01) BAM methods, respectively. Based on their good properties high thermal mechanical stabilities, these materials are potentially insensitive explosives.

Язык: Английский

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Energetic Cocrystallization as the Most Significant Crystal Engineering Way to Create New Energetic Materials

Crystal Growth & Design, Год журнала: 2022, Номер 22(2), С. 954 - 970

Опубликована: Янв. 13, 2022

Crystal engineering is a highly efficient way to create new materials with the desired properties. Energetic cocrystallization has been thriving for ∼10 years since appearance of series TNT-based energetic cocrystals (ECCs). ECCs serve as one important aspect crystal (EMs). This article presents brief overview regarding component, intermolecular interaction, packing structure, main properties, and preparation, well theoretical treatment some issues raised future development. In most cases, properties an ECC are each moderated between those pure components, setting basis tuning by existing molecules, instead synthesizing molecules; meanwhile, there also exceptions, such higher density, detonation or lower impact sensitivity in comparison both components. These exceptions mutated will expand EMs. Generally, currently staying at primary stage, much effort being required solve urgent issues, property evaluation, large-scale fabrication, applications. Still, promising alternative EMs after all, it huge challenge synthesize satisfactory molecule.

Язык: Английский

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Nitramine-Based Energetic Cocrystals with Improved Stability and Controlled Reactivity

Crystal Growth & Design, Год журнала: 2020, Номер 20(12), С. 8124 - 8147

Опубликована: Ноя. 11, 2020

The inherent contradiction between the energy density and safety of energetic materials (EMs) is very challenging. To solve this problem, cocrystallization technology has been usually used in field EMs to better balance safety. preparation techniques cocrystals mainly include solvent evaporation, solvent/nonsolvent, grinding methods. prepared by these methods have structures completely different from starting crystals. comprehensive performance (ECCs), such as density, solubility, sensitivity, thermal stability, significantly improved. This review summaries ECCs their fundamental formation mechanisms, where HMX-based CL-20-based are selected typical examples. Their structures, thermodynamic characteristics, detonation parameters summarized compared detail. Finally, future research directions challenges proposed based on literature survey.

Язык: Английский

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Molecular dynamics application of cocrystal energetic materials: A review

Nanotechnology Reviews, Год журнала: 2022, Номер 11(1), С. 2141 - 2153

Опубликована: Янв. 1, 2022

Abstract Cocrystallization is an important method to obtain high-energy and low-sensitivity explosives. Therefore, the synthesis, structures, properties of cocrystal energetic materials have become a highly active research topic. Studying physical chemical by molecular dynamics great significance for in-depth understanding design/synthesis new materials. This review introduces dynamics, synthesized successfully date, application The existing problems future development directions are discussed. We hope that this will encourage researchers interested in field design synthesize low-sensitive with practical value.

Язык: Английский

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Progress in Energy−Safety Balanced Cocrystallization of Four Commercially Attractive Nitramines

Crystal Growth & Design, Год журнала: 2024, Номер 24(17), С. 7361 - 7388

Опубликована: Авг. 19, 2024

In 2011, cocrystallization of energetic materials became a hot topic and pathway to overcome the energy−safety contradiction; especially for commercially attractive nitramines, it first preference researchers. The present review focuses on energetic−energetic four CL20, HMX, BCHMX, RDX, structural aspects these cocrystals, their influence thermochemical detonation properties. Cocrystallization has proven be crystal engineering technique achieve safety morphological suitability cocrystals (EECCs). Overall, in most cases, impact sensitivities EECCs are decreased, this is phenomenal change; however, needed adjust with properties slightly, negligible if coformer (EMs) properly chosen. There other notable variations morphologies packing crystals, including key such as relatively high density melting point. These changes occur due binding energy, trigger bond length, cohesive energy during cocrystallization. Researchers highly focused nitramines; earlier reported methods lacking selectivity scalability. When comes adoption industrial scale production EECCs, more difficult. We conducted thorough literature survey. Also we discussed about recently developed VPSZ coagglomeration method, which provides huge opportunity tune performance existing easy up level.

Язык: Английский

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Rapid Cocrystallization by Exploiting Differential Solubility: An Efficient and Scalable Process toward Easily Fabricating Energetic Cocrystals

Crystal Growth & Design, Год журнала: 2020, Номер 20(4), С. 2129 - 2134

Опубликована: Фев. 24, 2020

A new energetic cocrystal (1), composed of 1,3,5-trinitrobenzene (TNB) and 1-methyl-2,4-dinitroimidazole (2,4-MDNI), was synthesized for the first time via rapid cocrystallization by exploiting differential solubility. Further, this method extended to scale-up high-performance CL-20 (2,4,6,8,10,12-hexanitrohexaazaisowurt-zitane)/MTNP (1-methyl-3,4,5-trinitropyrazole) (2) on 100 g scale in a fast simple way, which is another larger preparation fields. The investigations thermodynamics kinetics coprecipitation crystallization indicate that solubility ratios pure components (R) associated with Gibbs free energy (ΔGform) offer valuable insights into selection suitable further design synthesis proposed method. Additionally, 2 exhibited good experimental comprehensive performances, making it potential candidate instead HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane) future. Hence, opens up an efficient, simple, scalable manufacture cocrystals high industrial production future practical applications.

Язык: Английский

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