Abstract
Three-dimensional (3D) printing has had a large impact on various fields, with fused deposition modeling (FDM) being the most versatile and cost-effective 3D printing technology. However, FDM often requires sacrificial support structures, which significantly complicates the processing and increases the cost. Furthermore, poor layer-to-layer adhesion greatly affects the mechanical stability of 3D-printed objects. Here, we present a new Print-Healing strategy to address the aforementioned challenges. A polymer ink (Cu-DOU-CPU) with synergetic triple dynamic bonds was developed to have excellent printability and room-temperature self-healing ability. Objects with various shapes were printed using a simple compact 3D printer, and readily assembled into large sophisticated architectures via self-healing. Triple dynamic bonds induce strong binding between layers. Additionally, damaged printed objects can spontaneously heal, which significantly elongates their service life. This work paves a simple and powerful way to solve the key bottlenecks in FDM 3D printing, and will have diverse applications.
摘要
3D打印已经在诸多领域产生了重要影响, 其中熔融沉积成 型(fused deposition modeling, FDM)是最通用和最经济的3D打印 技术. 然而, FDM通常需要支撑结构, 这大大增加了加工的复杂性 和成本. 此外, 层间结合力差极大地影响了FDM 3D打印制品的机 械稳定性. 本文提出了一种新的打印-愈合策略来解决上述挑战. 采 用了三重动态键设计, 研制了一种具有良好的打印性能和室温自 愈能力的聚合物. 利用简便紧凑型的3D打印机打印出了各种形状 的物体, 并通过自修复便捷地将它们组装成大型复杂的三维结构. 三重动态键显著提升了打印制品层与层之间的结合力. 此外, 损坏 的打印品可以自我修复, 这大大延长了它们的使用寿命. 这项工作 为解决FDM 3D打印的关键瓶颈问题提供了一种简单有效的方法, 有望在多个领域获得应用.
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References
MacDonald E, Wicker R. Multiprocess 3D printing for increasing component functionality. Science, 2016, 353: aaf2093
Zhang D, Jonhson W, Herng TS, et al. A 3D-printing method of fabrication for metals, ceramics, and multi-materials using a universal self-curable technique for robocasting. Mater Horiz, 2020, 7: 1083–1090
Zhu Z, Park HS, McAlpine MC. 3D printed deformable sensors. Sci Adv, 2020, 6: eaba5575
Wu T, Gray E, Chen B. A self-healing, adaptive and conductive polymer composite ink for 3D printing of gas sensors. J Mater Chem C, 2018, 6: 6200–6207
Gao F, Xu Z, Liang Q, et al. Osteochondral regeneration with 3D-printed biodegradable high-strength supramolecular polymer reinforced-gelatin hydrogel scaffolds. Adv Sci, 2019, 6: 1900867
Chen Q, Xu R, He Z, et al. Printing 3D gel polymer electrolyte in lithium-ion microbattery using stereolithography. J Electrochem Soc, 2017, 164: A1852–A1857
Conner BP, Manogharan GP, Martof AN, et al. Making sense of 3-D printing: Creating a map of additive manufacturing products and services. Addit Manuf, 2014, 1–4: 64–76
Gu Q, Zhu H, Li J, et al. Three-dimensional bioprinting speeds up smart regenerative medicine. Natl Sci Rev, 2016, 3: 331–344
Yang Y, Li X, Chu M, et al. Electrically assisted 3D printing of nacre-inspired structures with self-sensing capability. Sci Adv, 2019, 5: eaau9490
Chen Y, Zhuang X, Goldfine EA, et al. Printable organic-inorganic nanoscale multilayer gate dielectrics for thin-film transistors enabled by a polymeric organic interlayer. Adv Funct Mater, 2020, 30: 2005069
Zhang T, Zhou W, Jia Z, et al. Polydopamine-assisted functionalization of heparin and vancomycin onto microarc-oxidized 3D printed porous Ti6Al4V for improved hemocompatibility, osteogenic and anti-infection potencies. Sci China Mater, 2018, 61: 579–592
Liu J, Ye J, Pan F, et al. Solid-state yet flexible supercapacitors made by inkjet-printing hybrid ink of carbon quantum dots/graphene oxide platelets on paper. Sci China Mater, 2018, 62: 545–554
Alizadeh-Osgouei M, Li Y, Vahid A, et al. High strength porous PLA gyroid scaffolds manufactured via fused deposition modeling for tissue-engineering applications. Smart Mater Med, 2021, 2: 15–25
Senthil Kumar K, Chen PY, Ren H. A review of printable flexible and stretchable tactile sensors. Research, 2019, 2019: 1–32
Xu Y, Wu X, Guo X, et al. The boom in 3D-printed sensor technology. Sensors, 2017, 17: 1166
Wu L, Dong Z, Du H, et al. Bioinspired ultra-low adhesive energy interface for continuous 3D printing: Reducing curing induced adhesion. Research, 2018, 2018: 1–10
Truby RL, Lewis JA. Printing soft matter in three dimensions. Nature, 2016, 540: 371–378
Nadgorny M, Ameli A. Functional polymers and nanocomposites for 3D printing of smart structures and devices. ACS Appl Mater Interfaces, 2018, 10: 17489–17507
Yang K, Grant JC, Lamey P, et al. Diels-Alder reversible thermoset 3D printing: Isotropic thermoset polymers via fused filament fabrication. Adv Funct Mater, 2017, 27: 1700318
Lim J, Kim YK, Won DJ, et al. 3D printing of freestanding overhanging structures utilizing an in situ light guide. Adv Mater Technol, 2019, 4: 1900118
Gao Y, Wu L, Yan DM, et al. Near support-free multi-directional 3D printing via global-optimal decomposition. Graphical Model, 2019, 104: 101034
Asif M, Lee JH, Lin-Yip MJ, et al. A new photopolymer extrusion 5-axis 3D printer. Addit Manuf, 2018, 23: 355–361
Dai C, Wang CCL, Wu C, et al. Support-free volume printing by multi-axis motion. ACM Trans Graph, 2018, 37: 1–14
Kelly BE, Bhattacharya I, Heidari H, et al. Volumetric additive manufacturing via tomographic reconstruction. Science, 2019, 363: 1075–1079
Yang H, Li C, Yang M, et al. Printing hydrogels and elastomers in arbitrary sequence with strong adhesion. Adv Funct Mater, 2019, 29: 1901721
Shaffer S, Yang K, Vargas J, et al. On reducing anisotropy in 3D printed polymers via ionizing radiation. Polymer, 2014, 55: 5969–5979
Kuang X, Chen K, Dunn CK, et al. 3D printing of highly stretchable, shape-memory, and self-healing elastomer toward novel 4D printing. ACS Appl Mater Interfaces, 2018, 10: 7381–7388
Zhang B, Kowsari K, Serjouei A, et al. Reprocessable thermosets for sustainable three-dimensional printing. Nat Commun, 2018, 9: 1831
Wu Q, Zou S, Gosselin FP, et al. 3D printing of a self-healing nanocomposite for stretchable sensors. J Mater Chem C, 2018, 6: 12180–12186
Lai JC, Li L, Wang DP, et al. A rigid and healable polymer cross-linked by weak but abundant Zn(II)-carboxylate interactions. Nat Commun, 2018, 9: 2725
Zhang L, Liu Z, Wu X, et al. A highly efficient self-healing elastomer with unprecedented mechanical properties. Adv Mater, 2019, 31: 1901402
Rutz AL, Hyland KE, Jakus AE, et al. A multimaterial bioink method for 3D printing tunable, cell-compatible hydrogels. Adv Mater, 2015, 27: 1607–1614
Lei D, Yang Y, Liu Z, et al. A general strategy of 3D printing thermosets for diverse applications. Mater Horiz, 2019, 6: 394–404
Wu Q, Wei J, Xu B, et al. A robust, highly stretchable supramolecular polymer conductive hydrogel with self-healability and thermo-processability. Sci Rep, 2017, 7: 41566
He Y, Zhang X, Zhang X, et al. Structural investigations of toluene diisocyanate (TDI) and trimethylolpropane (TMP)-based polyurethane prepolymer. J Industrial Eng Chem, 2012, 18: 1620–1627
Cordier P, Tournilhac F, Soulié-Ziakovic C, et al. Self-healing and thermoreversible rubber from supramolecular assembly. Nature, 2008, 451: 977–980
Appuhamillage GA, Reagan JC, Khorsandi S, et al. 3D printed remendable polylactic acid blends with uniform mechanical strength enabled by a dynamic Diels-Alder reaction. Polym Chem, 2017, 8: 2087–2092
Davidson JR, Appuhamillage GA, Thompson CM, et al. Design paradigm utilizing reversible Diels-Alder reactions to enhance the mechanical properties of 3D printed materials. ACS Appl Mater Interfaces, 2016, 8: 16961–16966
Susa A, Bose RK, Grande AM, et al. Effect of the dianhydride/branched diamine ratio on the architecture and room temperature healing behavior of polyetherimides. ACS Appl Mater Interfaces, 2016, 8: 34068–34079
Li CH, Wang C, Keplinger C, et al. A highly stretchable autonomous self-healing elastomer. Nat Chem, 2016, 8: 618–624
Chen Y, Kushner AM, Williams GA, et al. Multiphase design of autonomic self-healing thermoplastic elastomers. Nat Chem, 2012, 4: 467–472
Rao YL, Chortos A, Pfattner R, et al. Stretchable self-healing polymeric dielectrics cross-linked through metal-ligand coordination. J Am Chem Soc, 2016, 138: 6020–6027
Lai JC, Jia XY, Wang DP, et al. Thermodynamically stable whilst kinetically labile coordination bonds lead to strong and tough self-healing polymers. Nat Commun, 2019, 10: 1164
Wu J, Cai LH, Weitz DA. Tough self-healing elastomers by molecular enforced integration of covalent and reversible networks. Adv Mater, 2017, 29: 1702616
Liu Z, Zhang L, Guan Q, et al. Biomimetic materials with multiple protective functionalities. Adv Funct Mater, 2019, 29: 1901058
Bapat AP, Sumerlin BS, Sutti A. Bulk network polymers with dynamic B-O bonds: Healable and reprocessable materials. Mater Horiz, 2020, 7: 694–714
Guo Q, Huang B, Lu C, et al. A cephalopod-inspired mechanoluminescence material with skin-like self-healing and sensing properties. Mater Horiz, 2019, 6: 996–1004
Deng XY, Xie H, Du L, et al. Polyurethane networks based on disulfide bonds: From tunable multi-shape memory effects to simultaneous self-healing. Sci China Mater, 2018, 62: 437–447
An XP, Chen JH, Li YD, et al. Rational design of sustainable polyurethanes from castor oil: Towards simultaneous reinforcement and toughening. Sci China Mater, 2018, 61: 993–1000
Acknowledgements
This work was supported by the National Natural Science Foundation of China (21991123, 52073049 and 51703148), the Natural Science Foundation of Shanghai (20ZR1402500 and 18ZR1401900), the Belt & Road Young Scientist Exchanges Project of Science and Technology Commission Foundation of Shanghai (20520741000), Shanghai Belt and Road Joint Laboratory of Advanced Fiber and Low-dimension Materials (Donghua University (DHU), 18520750400), and the Fundamental Research Funds for the Central Universities, DHU Distinguished Young Professor Program (LZA2019001), and the Open Research Fund of Shanghai Center for High-performance Fibers and Composites and the Center for Civil Aviation Composites of Donghua University.
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Zuo H, Wu Q and You Z conceived the idea and designed the experiments. You Z directed the entire project. Zuo H performed the experiments (with involvement of Liu Z, Zhang L, Liu G and Ouyang X). Zuo H, Liu Z, Zhang L, Guan Q and Wu Q contributed to data analysis and interpretation. Zuo H and You Z wrote the manuscript. All authors commented on the manuscript.
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The authors declare that they have no conflict of interest.
Han Zuo is a PhD student at the State Key Laboratory for Modification of Chemical Fibers and Polymer Materials at Donghua University. From 2016 to now, she has been conducting her master and doctoral research at Donghua University. Her current research involves biomaterials, 3D printing and self-healing polymers.
Zhengwei You is a professor and the chair of the Department of Composite Materials at Donghua University. He serves as the director of Research Base of Textile Materials for Flexible Electronics and Biomedical Applications, China Textile Engineering Society. He received his PhD degree from Shanghai Institute of Organic Chemistry and conducted research at Georgia Institute of Technology, University of Pittsburgh, and Bayer MaterialScience. His current research involves elastomers, biomaterials, 3D printing, and stretchable electronics.
Qilin Wu received her PhD degree from Donghua University in 2002. As a visiting scholar, she worked at the University of California, Davis for one year from 2006 to 2007. Now she is a full professor of Donghua University. Her research focuses on composite materials.
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Zuo, H., Liu, Z., Zhang, L. et al. Self-healing materials enable free-standing seamless large-scale 3D printing. Sci. China Mater. 64, 1791–1800 (2021). https://doi.org/10.1007/s40843-020-1603-y
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DOI: https://doi.org/10.1007/s40843-020-1603-y