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通过甲基丙烯酸酯化和共混将羟丙基纤维素直接墨水书写并光交联成稳定的三维部件

Direct Ink Writing and Photocrosslinking of Hydroxypropyl Cellulose into Stable 3D Parts Using Methacrylation and Blending.

作者信息

Yapa Mehmet-Talha, Sivasankarapillai Gopakumar, Lalevée Jacques, Laborie Marie-Pierre

机构信息

Chair of Forest Biomaterials, Institute of Earth and Environmental Sciences, Faculty of Environment and Natural Resources, University of Freiburg, Werthmanstr. 6, 79085 Freiburg im Breisgau, Germany.

Freiburg Materials Research Center, Stefan-Meier-Straße 21, 79104 Freiburg im Breisgau, Germany.

出版信息

Polymers (Basel). 2025 Jan 22;17(3):278. doi: 10.3390/polym17030278.

Abstract

Two 50% solid content solutions of methacrylated hydroxypropyl cellulose (MAHPC) with respective substitution degrees of 1.85 ± 0.04 (L_MAHPC) and 2.64 ± 0.04 (H_MAHPC) were screened for rheological properties, photocrosslinking kinetics and printability in relevance to direct ink writing (DIW). Photo-rheological and printability studies reveal that the rheological properties of both MAHPC inks are better suited for DIW than those of hydroxypropyl cellulose (HPC) inks. Namely, methacrylate grafting improves shear dynamic moduli at low strain but also shear thinning and shear recovery. Both inks completely cure within 30 s upon shining UV light. Photocrosslinking is found to follow the phenomenological autocatalytic Sestak-Berggren kinetic model. However, prolonged exposure to UV light past full cure upon DIW leads to part fracture. The narrow UV-cure time window consequently precludes the production of multilayer parts using UV-assisted DIW for these neat MAHPC inks. In contrast, when blending MAHPC with HPC, an optimal balance between curing kinetics and DIW conditions is achieved, and stable, high-fidelity 150-layered parts are produced. Altogether this research highlights the need to design the content of photocrosslinkable moieties of cellulose derivatives to photoprint high fidelity and stable 3D parts from HPC inks.

摘要

筛选了两种甲基丙烯酸酯化羟丙基纤维素(MAHPC)的50%固含量溶液,其取代度分别为1.85±0.04(L_MAHPC)和2.64±0.04(H_MAHPC),研究其与直接墨水书写(DIW)相关的流变性能、光交联动力学和可打印性。光流变学和可打印性研究表明,与羟丙基纤维素(HPC)墨水相比,两种MAHPC墨水的流变性能更适合DIW。也就是说,甲基丙烯酸酯接枝在低应变下提高了剪切动态模量,但也改善了剪切变稀和剪切恢复性能。两种墨水在照射紫外光后30秒内完全固化。发现光交联遵循唯象自催化Sestak-Berggren动力学模型。然而,在DIW完全固化后长时间暴露于紫外光会导致部件断裂。因此,对于这些纯MAHPC墨水,狭窄的紫外光固化时间窗口排除了使用紫外辅助DIW生产多层部件的可能性。相比之下,当将MAHPC与HPC混合时,在固化动力学和DIW条件之间实现了最佳平衡,并生产出了稳定的、高保真的150层部件。总之,这项研究强调了设计纤维素衍生物光可交联部分的含量,以便从HPC墨水中光打印高保真和稳定的3D部件的必要性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/87c2/11821224/fd2d74672c70/polymers-17-00278-sch001.jpg

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