Shreyasi Banik, Richa Rajak, Jean'ne M. Shreeve, Srinivas Dharavath
{"title":"Exploring Green Pyrotechnic Formulations and Primary Explosives with 1,3,4-Oxadiazole-Based Micro and Submicron Energetic Coordination Polymers","authors":"Shreyasi Banik, Richa Rajak, Jean'ne M. Shreeve, Srinivas Dharavath","doi":"10.1002/smll.202409255","DOIUrl":null,"url":null,"abstract":"<p>Alkali and alkaline-earth metal incorporated 5,5′-dinitramino-3,3′-azo-1,3,4-oxadiazole (H<sub>2</sub>DNAO) based Energetic Coordination Polymers (ECPs), namely dipotassium 5,5′-dinitramino-3,3′-azo-1,3,4-oxadiazole(K<sub>2</sub>DNAO), dicesium 5,5′-dinitramino-3,3′-azo-1,3,4-oxadiazole(Cs<sub>2</sub>DNAO) and barium 5,5′-dinitramino-3,3′-azo-1,3,4-oxadiazole(BaDNAO) are synthesized for the first time. Synthesized ECPs are thoroughly characterized using infrared spectroscopy (IR), elemental analysis (EA), thermogravimetric analysis and differential scanning calorimetry (TGA-DSC), field emission scanning electron microscopy (FE-SEM), and dynamic light scattering (DLS), UV–vis spectroscopy. All ECPs are also confirmed by single-crystal X-ray diffraction technique (SC-XRD). The micro-ECPs exhibit excellent densities (1.98–2.80 g cm<sup>−3</sup>), insensitivities (IS: 25-40 J; FS: 240-360 N), and good thermal stabilities (<i>T</i><sub>d</sub>: 182–212 °C). K<sub>2</sub>DNAO and Cs<sub>2</sub>DNAO show good detonation performance (VOD:7460-7893 m s<sup>−1</sup>; DP: 27.5-30.6 GPa), respectively. To further investigate sub-micron-energetics, three sub-micron ECPs are prepared from their micro counterparts using ultrasonication method, demonstrating significant improvement in thermal stability (<i>T</i><sub>d</sub>: 194–221 °C) but are highly sensitivity (IS: 2-15J; FS: 40-360N). Burning tests of two experimental formulations using micro K<sub>2</sub>DNAO and Cs<sub>2</sub>DNAO demonstrate their potential in green pyrotechnic applications. Interestingly, the submicron-counterparts show remarkable initiating capability. Considering their ease of synthesis, and safety profile, these materials can be effectively transported in their microform and can be rapidly converted into submicron-form on demand, making them suitable for pyrotechnic applications.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":"21 9","pages":""},"PeriodicalIF":13.0000,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Small","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/smll.202409255","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Alkali and alkaline-earth metal incorporated 5,5′-dinitramino-3,3′-azo-1,3,4-oxadiazole (H2DNAO) based Energetic Coordination Polymers (ECPs), namely dipotassium 5,5′-dinitramino-3,3′-azo-1,3,4-oxadiazole(K2DNAO), dicesium 5,5′-dinitramino-3,3′-azo-1,3,4-oxadiazole(Cs2DNAO) and barium 5,5′-dinitramino-3,3′-azo-1,3,4-oxadiazole(BaDNAO) are synthesized for the first time. Synthesized ECPs are thoroughly characterized using infrared spectroscopy (IR), elemental analysis (EA), thermogravimetric analysis and differential scanning calorimetry (TGA-DSC), field emission scanning electron microscopy (FE-SEM), and dynamic light scattering (DLS), UV–vis spectroscopy. All ECPs are also confirmed by single-crystal X-ray diffraction technique (SC-XRD). The micro-ECPs exhibit excellent densities (1.98–2.80 g cm−3), insensitivities (IS: 25-40 J; FS: 240-360 N), and good thermal stabilities (Td: 182–212 °C). K2DNAO and Cs2DNAO show good detonation performance (VOD:7460-7893 m s−1; DP: 27.5-30.6 GPa), respectively. To further investigate sub-micron-energetics, three sub-micron ECPs are prepared from their micro counterparts using ultrasonication method, demonstrating significant improvement in thermal stability (Td: 194–221 °C) but are highly sensitivity (IS: 2-15J; FS: 40-360N). Burning tests of two experimental formulations using micro K2DNAO and Cs2DNAO demonstrate their potential in green pyrotechnic applications. Interestingly, the submicron-counterparts show remarkable initiating capability. Considering their ease of synthesis, and safety profile, these materials can be effectively transported in their microform and can be rapidly converted into submicron-form on demand, making them suitable for pyrotechnic applications.
期刊介绍:
Small serves as an exceptional platform for both experimental and theoretical studies in fundamental and applied interdisciplinary research at the nano- and microscale. The journal offers a compelling mix of peer-reviewed Research Articles, Reviews, Perspectives, and Comments.
With a remarkable 2022 Journal Impact Factor of 13.3 (Journal Citation Reports from Clarivate Analytics, 2023), Small remains among the top multidisciplinary journals, covering a wide range of topics at the interface of materials science, chemistry, physics, engineering, medicine, and biology.
Small's readership includes biochemists, biologists, biomedical scientists, chemists, engineers, information technologists, materials scientists, physicists, and theoreticians alike.