A scalable exfoliating approach to achieve high-quality shell nanosheets with large lateral size and surface functionalization

Yuansen Liu , Qi Wu , Xinqing Zheng , Min Nie
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Abstract

With rapid development of global marine aquaculture, large amounts of waste shellfish as an aquaculture by-product are generated after consumption. At present, waste seashell powder (WSP) as fillers mixed with polymers is a potentially efficient method to add-value recycle WSP, but the poorly compatibility and seriously agglomeration of WSP results in the low mechanical properties and then reduces the value of recycled shell-based products. In this study, a facile ball-milling exfoliation method with the assistance of polyethyleneimine (PEI) to exfoliate shell materials into high-quality shell nanosheets (SNs) is present. In this case, PEI macromolecular had dual function: it not only acted as a buffer between milling balls and WSP to prevent excessive breaking of the WSP, but also interacted with active bonds on the surface to functionalize the SNs. As a demonstration, the high quality SNs achieve an average lateral size of 414 nm and thickness of 5 nm. Furthermore, the grafting of hydroxyl and amine functional groups onto the SNs, along with the low surface energy of the resulting SNs, has the potential to enhance interfacial interactions with the polymer matrix, thus promoting the overall performance of shell-based composites. This work presents a green and scalable approach for the value-added recycling of waste seashells, offering a sustainable solution to address the environmental impact of aquaculture by-products.
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实现大横向尺寸和表面功能化的高质量壳纳米片的可扩展剥离方法
随着全球海水养殖业的快速发展,大量废弃贝类作为养殖副产品被消耗后产生。目前,将废弃贝壳粉(WSP)作为填料与聚合物混合是实现废弃贝壳粉增值再利用的一种潜在有效方法,但由于废弃贝壳粉相容性差、团聚严重,导致其机械性能低下,进而降低了再生贝壳基产品的价值。本研究采用球磨剥离法,在聚乙烯亚胺(PEI)的辅助下将贝壳材料剥离成高质量的贝壳纳米片(SN)。在这种情况下,聚乙烯亚胺大分子具有双重功能:它不仅在研磨球和 WSP 之间起缓冲作用,防止 WSP 过度破碎,还能与表面的活性键相互作用,使 SN 功能化。结果表明,高质量 SN 的平均横向尺寸为 414 nm,厚度为 5 nm。此外,羟基和胺官能团接枝到 SNs 上,加上所产生 SNs 的低表面能,有可能增强与聚合物基体的界面相互作用,从而提高壳基复合材料的整体性能。这项工作为废弃贝壳的增值回收提供了一种绿色、可扩展的方法,为解决水产养殖副产品对环境的影响提供了一种可持续的解决方案。
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