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通过衣康酸聚酯接枝增强3D打印氧化石墨烯纳米复合材料的性能

Enhanced Properties of 3D-Printed Graphene Oxide Nanocomposites through Itaconic Acid Polyester Grafting.

作者信息

Maturi Mirko, Maturi Simone, Sanz de León Alberto, Migliorini Lorenzo, de la Mata María, Benelli Tiziana, Giorgini Loris, Milani Paolo, Comes Franchini Mauro, Molina Sergio Ignacio

机构信息

Dpto. Ciencia de los Materiales, I. M. y Q. I., IMEYMAT, Facultad de Ciencias, Universidad de Cádiz, 11510 Puerto Real, Cádiz, Spain.

Department of Industrial Chemistry "Toso Montanari", University of Bologna, Via P. Gobetti 85, Bologna 40129, Italy.

出版信息

ACS Appl Polym Mater. 2025 Mar 28;7(7):4371-4382. doi: 10.1021/acsapm.5c00014. eCollection 2025 Apr 11.

Abstract

Vat photopolymerization (VP) is a powerful additive manufacturing process to produce high-resolution 3D objects from liquid photocurable resins, but the mechanical performance of its standard materials restricts its use in high-demanding applications. In this study, graphene oxide (GO), a widely investigated nanomaterial, was surface-functionalized by grafting the sustainable and photocurable poly-(butylene itaconate--adipate) (PBIA) polyester to address these limitations. The covalent grafting of PBIA significantly improved the colloidal stability and dispersibility of GO in photocurable formulations, eliminating the need for extensive homogenization during the formulation of the nanocomposite resin. PBIA-coated GO (GO@PBIA) was easily miscible with VP resins, enabling the fabrication of 3D-printed nanocomposites with superior mechanical properties. At low filler concentrations (0.05 wt %), the GO@PBIA composites increased their elastic modulus up to 57% and tensile strength up to 100% compared to the base polymer, outperforming analogous composites prepared with unmodified GO. Surface modification also enhanced the deformability of the matrix, making these composites suitable for applications under tensile and flexural loads. Optical and morphological analyses confirmed the homogeneous distribution of GO@PBIA within the polymer matrix, demonstrating improved filler-matrix interactions, while electrical conductivity measurements proved that the surface modification approach proposed does not affect the conductive conjugated π system of the nanomaterial. This work highlights the potential of polymer-grafted GO as a multifunctional nanofiller to enhance the mechanical properties and processability of VP-based materials, paving the way for their use in high-performance applications.

摘要

光聚合(VP)是一种强大的增材制造工艺,可从液体光固化树脂中生产高分辨率的3D物体,但其标准材料的机械性能限制了其在高要求应用中的使用。在本研究中,通过接枝可持续且可光固化的聚(衣康酸丁二酯-己二酸酯)(PBIA)聚酯对广泛研究的纳米材料氧化石墨烯(GO)进行表面功能化,以解决这些限制。PBIA的共价接枝显著提高了GO在光固化配方中的胶体稳定性和分散性,消除了在纳米复合树脂配方过程中进行大量均质化的需要。PBIA包覆的GO(GO@PBIA)很容易与VP树脂混溶,从而能够制造出具有优异机械性能的3D打印纳米复合材料。在低填料浓度(0.05 wt%)下,与基础聚合物相比,GO@PBIA复合材料的弹性模量提高了57%,拉伸强度提高了100%,优于用未改性GO制备的类似复合材料。表面改性还增强了基体的可变形性,使这些复合材料适用于拉伸和弯曲载荷下的应用。光学和形态分析证实了GO@PBIA在聚合物基体中的均匀分布,表示填料与基体之间的相互作用得到改善,而电导率测量证明所提出的表面改性方法不会影响纳米材料的导电共轭π体系。这项工作突出了聚合物接枝GO作为多功能纳米填料增强基于VP的材料的机械性能和可加工性的潜力,为其在高性能应用中的使用铺平了道路。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c624/12150230/9381a73939d0/ap5c00014_0001.jpg

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