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• W2023677079 abstract "The ages of time have been named for materials. We advanced from the Stone Age beyond the Bronze and Iron Ages by discovering the beneficial effects of non-uniformity in materials, including additives, compounds, mixtures, and dopants. Today, many technologies that impact our daily quality of life rely on deliberate engineering of these non-uniformities or defects. Doped silicon and steel are examples of the influence of deliberate property changes through impurities, and the ability to adjust the hardness of copper through working is an example of mechanical changes induced through dislocation content. These examples clearly convey the power of controlling defects. Clever engineering of traditional materials such as metals, polymers and ceramics has gradually arisen from decades or centuries of research and experience. Energetic materials have made similar leaps in safety and performance through the mixing of materials. Stabilization of nitroglycerin, energy enhancement of melt-processed TNT through eutectic mixtures, and alteration of blast profiles through metal additions to formulations are a few examples. We are on the verge of revolutionary advances as we begin to understand and control mixtures at the molecular level. Many propellants, explosives, and pyrotechnics are crystalline, molecular materials. This class of materials has many other industrially important applications, including pharmaceuticals, foods, dyes, optics, and electronics. Surprisingly, only within the last 10 years have some of the fundamental materials properties of these crystalline explosives been measured. The needed samples are difficult to prepare, the measurements are often not suited to molecular materials, and the materials themselves have characteristically low symmetry and fragility. However, new diagnostics are enabling us to reveal the location and mechanisms of defects, and the exploration of co-crystals will deliver truly unique materials properties from new and old molecules. Crystal engineering will bring true materials by design capability to energetic material for the first time. There is a renewed, worldwide, focus on crystallization to address recognized needs in both scientific samples and industrial applications. Crystal samples are becoming more readily available as a result, and multiple measurements of properties have sometimes been made. With hindsight, it is not surprising that results are highly specific to how the individual crystals or crystalline powders are made and processed. These property differences, which are sometimes quite large, are likely due to differences in defect content, type, and structure, although the mechanistic connections are still not understood. But there is something more. We have started to see a surge of papers on co-crystalline explosives. While differing definitions are in the literature, a co-crystal is generally defined as a unique crystalline form that contains two or more unique neutral molecules (not salts) that are normally solid at room temperature (not solvates). A metallurgist would call these compounds on a phase diagram, but since that term has a different meaning for chemists, the term co-crystal was coined. Co-crystals have been known for many years, but received a surge of interest from the pharmaceutical community beginning approximately 15 years ago. Significant changes to properties, including solubility and mechanical behavior, have been demonstrated in co-crystals of active pharmaceutical ingredients. In the energetic materials community, papers on co-crystals are starting to increase in frequency, and it is likely that many more will appear over the coming years. Several have already appeared in PEP, and I suspect you will see many more both in these pages and throughout the literature. Learning how the defects influence molecular crystal properties is a very important goal; all of the “good stuff” in materials science arises from understanding and controlling these defect structures. The same tools developed for co-crystal discovery and characterization will also enable new understanding of the effects of impurities and defects. In the rush to discover new co-crystals, we should not forget the power of using the whole phase diagram to significantly alter properties. The Crystal Engineering Age has arrived for propellants, explosives, and pyrotechnics. Daniel E. Hooks Los Alamos National Laboratory Los Alamos, NM USA" @default.
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• W2023677079 date "2013-12-01" @default.
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• W2023677079 title "Editorial: Crystal Engineering in Energetic Materials" @default.
• W2023677079 doi "https://doi.org/10.1002/prep.201380631" @default.
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