3D printable colloidal dispersions demonstrating sol-to-gel transition at low silica concentrations mediated by molecular weight distribution of polypropylene glycol oligomer

Thixotropic colloidal gels composed by hydrophilic silica and polypropylene glycol (PPG) oligomer fluidize upon shear and solidify upon cease of flow, facilitating their use in 3D printing. In this study, we present a novel approach to high-fidelity 3D printing that leverages a dual-stream mixing te...

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Main Authors: Sai Wu, Qingxu Zhang, Shihao Xiao, Li'an Zhang, Chaoyi Fan, Jinpeng Wang, Jian Wang, Yijun Shen, Yihu Song, Qiang Zheng
Format: Article
Language:English
Published: Elsevier 2025-04-01
Series:Giant
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Online Access:http://www.sciencedirect.com/science/article/pii/S2666542525000025
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author Sai Wu
Qingxu Zhang
Shihao Xiao
Li'an Zhang
Chaoyi Fan
Jinpeng Wang
Jian Wang
Yijun Shen
Yihu Song
Qiang Zheng
author_facet Sai Wu
Qingxu Zhang
Shihao Xiao
Li'an Zhang
Chaoyi Fan
Jinpeng Wang
Jian Wang
Yijun Shen
Yihu Song
Qiang Zheng
author_sort Sai Wu
collection DOAJ
description Thixotropic colloidal gels composed by hydrophilic silica and polypropylene glycol (PPG) oligomer fluidize upon shear and solidify upon cease of flow, facilitating their use in 3D printing. In this study, we present a novel approach to high-fidelity 3D printing that leverages a dual-stream mixing technique within the printer nozzle for the first time. This innovative method enables the precise fabrication of colloidal objects even at low volume fractions (φ) of filler. The printed gels, containing a pre-stored crosslinker, can be further processed into polyurethane nanocomposites, broadening their potential applications. Rheological studies demonstrate that the sol-gel transition in these systems can be effectively controlled by adjusting the molecular weight distribution of the polydisperse PPG oligomers. This investigation has led to the creation of a comprehensive polydispersity-molecular weight-φ phase diagram that characterizes the behavior of the gels under different conditions. Moreover, the mechanistic studies reveal that gelation of polydisperse oligomers occurs at significantly lower φ compared to monodisperse systems, which is attributed to the formation of thicker glassy layers surrounding the silica nanoparticles. Our findings provide valuable insights into the design and optimization of thixotropic gels, making them promising candidates for various applications requiring precise rheological control in materials science.
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institution DOAJ
issn 2666-5425
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publishDate 2025-04-01
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spelling doaj-art-b265436db8bb40c08cf32012ba3036a82025-08-20T03:08:32ZengElsevierGiant2666-54252025-04-012210035310.1016/j.giant.2025.1003533D printable colloidal dispersions demonstrating sol-to-gel transition at low silica concentrations mediated by molecular weight distribution of polypropylene glycol oligomerSai Wu0Qingxu Zhang1Shihao Xiao2Li'an Zhang3Chaoyi Fan4Jinpeng Wang5Jian Wang6Yijun Shen7Yihu Song8Qiang Zheng9College of Chemistry and Materials Engineering, Zhejiang A&F University, Hangzhou 311300, China; Corresponding authors.MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China; Zhejiang HaiNa Semiconductor Co., Ltd., Quzhou 324300, ChinaZhejiang HaiNa Semiconductor Co., Ltd., Quzhou 324300, ChinaZhejiang HaiNa Semiconductor Co., Ltd., Quzhou 324300, ChinaCollege of Chemistry and Materials Engineering, Zhejiang A&F University, Hangzhou 311300, ChinaCollege of Chemistry and Materials Engineering, Zhejiang A&F University, Hangzhou 311300, ChinaCollege of Chemistry and Materials Engineering, Zhejiang A&F University, Hangzhou 311300, ChinaZhejiang HaiNa Semiconductor Co., Ltd., Quzhou 324300, China; Corresponding authors.MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China; Corresponding authors.MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, ChinaThixotropic colloidal gels composed by hydrophilic silica and polypropylene glycol (PPG) oligomer fluidize upon shear and solidify upon cease of flow, facilitating their use in 3D printing. In this study, we present a novel approach to high-fidelity 3D printing that leverages a dual-stream mixing technique within the printer nozzle for the first time. This innovative method enables the precise fabrication of colloidal objects even at low volume fractions (φ) of filler. The printed gels, containing a pre-stored crosslinker, can be further processed into polyurethane nanocomposites, broadening their potential applications. Rheological studies demonstrate that the sol-gel transition in these systems can be effectively controlled by adjusting the molecular weight distribution of the polydisperse PPG oligomers. This investigation has led to the creation of a comprehensive polydispersity-molecular weight-φ phase diagram that characterizes the behavior of the gels under different conditions. Moreover, the mechanistic studies reveal that gelation of polydisperse oligomers occurs at significantly lower φ compared to monodisperse systems, which is attributed to the formation of thicker glassy layers surrounding the silica nanoparticles. Our findings provide valuable insights into the design and optimization of thixotropic gels, making them promising candidates for various applications requiring precise rheological control in materials science.http://www.sciencedirect.com/science/article/pii/S2666542525000025Colloidal dispersionsSol-to-gel transitionMolecular weight distribution3D printing
spellingShingle Sai Wu
Qingxu Zhang
Shihao Xiao
Li'an Zhang
Chaoyi Fan
Jinpeng Wang
Jian Wang
Yijun Shen
Yihu Song
Qiang Zheng
3D printable colloidal dispersions demonstrating sol-to-gel transition at low silica concentrations mediated by molecular weight distribution of polypropylene glycol oligomer
Giant
Colloidal dispersions
Sol-to-gel transition
Molecular weight distribution
3D printing
title 3D printable colloidal dispersions demonstrating sol-to-gel transition at low silica concentrations mediated by molecular weight distribution of polypropylene glycol oligomer
title_full 3D printable colloidal dispersions demonstrating sol-to-gel transition at low silica concentrations mediated by molecular weight distribution of polypropylene glycol oligomer
title_fullStr 3D printable colloidal dispersions demonstrating sol-to-gel transition at low silica concentrations mediated by molecular weight distribution of polypropylene glycol oligomer
title_full_unstemmed 3D printable colloidal dispersions demonstrating sol-to-gel transition at low silica concentrations mediated by molecular weight distribution of polypropylene glycol oligomer
title_short 3D printable colloidal dispersions demonstrating sol-to-gel transition at low silica concentrations mediated by molecular weight distribution of polypropylene glycol oligomer
title_sort 3d printable colloidal dispersions demonstrating sol to gel transition at low silica concentrations mediated by molecular weight distribution of polypropylene glycol oligomer
topic Colloidal dispersions
Sol-to-gel transition
Molecular weight distribution
3D printing
url http://www.sciencedirect.com/science/article/pii/S2666542525000025
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