Three-Dimensional Printable, Extremely Soft, Stretchable, and Reversible Elastomers from Molecular Architecture-Directed Assembly

Nian, Shifeng; Zhu, Jinchang; Zhang, Haozhe; Gong, Zihao; Freychet, Guillaume; Zhernenkov, Mikhail; Xu, Baoxing; Cai, Li-Heng

doi:10.1021/acs.chemmater.0c04659

Three-Dimensional Printable, Extremely Soft, Stretchable, and Reversible Elastomers from Molecular Architecture-Directed Assembly

Journal Article · Wed Mar 31 00:00:00 EDT 2021 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.0c04659· OSTI ID:1778811

^[1]; Zhu, Jinchang ^[1]; Zhang, Haozhe ^[2]; Gong, Zihao ^[1]; Freychet, Guillaume ^[3]; ^[3]; ^[2]; ^[4]

Univ. of Virginia, Charlottesville, VA (United States). Soft Biomatter Lab.
Univ. of Virginia, Charlottesville, VA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Univ. of Virginia, Charlottesville, VA (United States). Soft Biomatter Lab.; Univ. of Virginia, Charlottesville, VA (United States)

3D printing elastomers enables the fabrication of many technologically important structures and devices such as tissue scaffolds, sensors, actuators, and soft robots. However, conventional 3D printable elastomers are intrinsically stiff; moreover, the process of printing often requires external mechanical support and/or post-treatment. In this work, we exploit the self-assembly of a responsive linear-bottlebrush-linear triblock copolymer to create stimuli-reversible, extremely soft, and stretchable elastomers and demonstrate their applicability as inks for in situ direct-write printing 3D structures without the aid of external mechanical support or post-treatment. By developing a procedure for controlled synthesis of such architecturally designed block copolymers, we create elastomers with extensibility up to 600% and Young’s moduli down to ~10² Pa, 10⁶ times softer than plastics and more than 102 times softer than all existing 3D printable elastomers. Moreover, the elastomers are thermostable and remain to be solid up to 180 °C, yet they are 100% solvent-reprocessable. Their extreme softness, stretchability, thermostability, and solvent-reprocessability bode well for future applications.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1778811

Report Number(s):: BNL--221305-2021-JAAM

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 7 Vol. 33; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (51)

Molecularly-Engineered, 4D-Printed Liquid Crystal Elastomer Actuators Saed, Mohand O.; Ambulo, Cedric P.; Kim, Hyun Advanced Functional Materials, Vol. 29, Issue 3 https://doi.org/10.1002/adfm.201806412	journal	November 2018
3D Printed Multifunctional, Hyperelastic Silicone Rubber Foam Chen, Qiyi; Zhao, Jiayu; Ren, Jingbo Advanced Functional Materials, Vol. 29, Issue 23 https://doi.org/10.1002/adfm.201900469	journal	April 2019
Block Copolymer Nanocomposites: Perspectives for Tailored Functional Materials Bockstaller, M. R.; Mickiewicz, R. A.; Thomas, E. L. Advanced Materials, Vol. 17, Issue 11, p. 1331-1349 https://doi.org/10.1002/adma.200500167	journal	June 2005
3D Bioprinting of Vascularized, Heterogeneous Cell-Laden Tissue Constructs Kolesky, David B.; Truby, Ryan L.; Gladman, A. Sydney Advanced Materials, Vol. 26, Issue 19 https://doi.org/10.1002/adma.201305506	journal	February 2014
Embedded 3D Printing of Strain Sensors within Highly Stretchable Elastomers Muth, Joseph T.; Vogt, Daniel M.; Truby, Ryan L. Advanced Materials, Vol. 26, Issue 36, p. 6307-6312 https://doi.org/10.1002/adma.201400334	journal	June 2014
Direct 3D Printing of Shear-Thinning Hydrogels into Self-Healing Hydrogels Highley, Christopher B.; Rodell, Christopher B.; Burdick, Jason A. Advanced Materials, Vol. 27, Issue 34 https://doi.org/10.1002/adma.201501234	journal	July 2015
Soft Poly(dimethylsiloxane) Elastomers from Architecture-Driven Entanglement Free Design Cai, Li-Heng; Kodger, Thomas E.; Guerra, Rodrigo E. Advanced Materials, Vol. 27, Issue 35 https://doi.org/10.1002/adma.201502771	journal	August 2015
Highly Stretchable and UV Curable Elastomers for Digital Light Processing Based 3D Printing Patel, Dinesh K.; Sakhaei, Amir Hosein; Layani, Michael Advanced Materials, Vol. 29, Issue 15 https://doi.org/10.1002/adma.201606000	journal	February 2017
3D Printing of Liquid Crystal Elastomeric Actuators with Spatially Programed Nematic Order Kotikian, Arda; Truby, Ryan L.; Boley, John William Advanced Materials, Vol. 30, Issue 10 https://doi.org/10.1002/adma.201706164	journal	January 2018
3D Printable and Reconfigurable Liquid Crystal Elastomers with Light‐Induced Shape Memory via Dynamic Bond Exchange Davidson, Emily C.; Kotikian, Arda; Li, Shucong Advanced Materials, Vol. 32, Issue 1 https://doi.org/10.1002/adma.201905682	journal	October 2019
Liquid‐Crystal‐Elastomer‐Based Dissipative Structures by Digital Light Processing 3D Printing Traugutt, Nicholas A.; Mistry, Devesh; Luo, Chaoqian Advanced Materials, Vol. 32, Issue 28 https://doi.org/10.1002/adma.202000797	journal	June 2020
Glass temperatures of some acrylic polymers Krause, Sonja; Gormley, James J.; Roman, Nicholas Journal of Polymer Science Part A: General Papers, Vol. 3, Issue 10 https://doi.org/10.1002/pol.1965.100031020	journal	October 1965
A review of nonlinear oscillatory shear tests: Analysis and application of large amplitude oscillatory shear (LAOS) Hyun, Kyu; Wilhelm, Manfred; Klein, Christopher O. Progress in Polymer Science, Vol. 36, Issue 12 https://doi.org/10.1016/j.progpolymsci.2011.02.002	journal	December 2011
Strategies and Molecular Design Criteria for 3D Printable Hydrogels Jungst, Tomasz; Smolan, Willi; Schacht, Kristin Chemical Reviews, Vol. 116, Issue 3 https://doi.org/10.1021/acs.chemrev.5b00303	journal	October 2015
Polymers for 3D Printing and Customized Additive Manufacturing Ligon, Samuel Clark; Liska, Robert; Stampfl, Jürgen Chemical Reviews, Vol. 117, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00074	journal	July 2017
Remarkable Effect of Molecular Architecture on Chain Exchange in Triblock Copolymer Micelles Lu, Jie; Bates, Frank S.; Lodge, Timothy P. Macromolecules, Vol. 48, Issue 8 https://doi.org/10.1021/acs.macromol.5b00294	journal	April 2015
Comparison of Gel Relaxation Times and End-Block Pullout Times in ABA Triblock Copolymer Networks Peters, Andrew J.; Lodge, Timothy P. Macromolecules, Vol. 49, Issue 19 https://doi.org/10.1021/acs.macromol.6b01921	journal	September 2016
3D Printing of Highly Stretchable, Shape-Memory, and Self-Healing Elastomer toward Novel 4D Printing Kuang, Xiao; Chen, Kaijuan; Dunn, Conner K. ACS Applied Materials & Interfaces, Vol. 10, Issue 8 https://doi.org/10.1021/acsami.7b18265	journal	February 2018
3D Printing Latex: A Route to Complex Geometries of High Molecular Weight Polymers Scott, Philip J.; Meenakshisundaram, Viswanath; Hegde, Maruti ACS Applied Materials & Interfaces, Vol. 12, Issue 9 https://doi.org/10.1021/acsami.9b19986	journal	February 2020
3D Printing PDMS Elastomer in a Hydrophilic Support Bath via Freeform Reversible Embedding Hinton, Thomas J.; Hudson, Andrew; Pusch, Kira ACS Biomaterials Science & Engineering, Vol. 2, Issue 10 https://doi.org/10.1021/acsbiomaterials.6b00170	journal	May 2016
Molecular Architecture Directs Linear–Bottlebrush–Linear Triblock Copolymers to Self-Assemble to Soft Reprocessable Elastomers Nian, Shifeng; Lian, Huada; Gong, Zihao ACS Macro Letters, Vol. 8, Issue 11 https://doi.org/10.1021/acsmacrolett.9b00721	journal	October 2019
Self-Assembly and Stress Relaxation in Acrylic Triblock Copolymer Gels Seitz, Michelle E.; Burghardt, Wesley R.; Faber, K. T. Macromolecules, Vol. 40, Issue 4 https://doi.org/10.1021/ma061993+	journal	January 2007
Printing soft matter in three dimensions Truby, Ryan L.; Lewis, Jennifer A. Nature, Vol. 540, Issue 7633 https://doi.org/10.1038/nature21003	journal	December 2016
3D bioprinting of tissues and organs Murphy, Sean V.; Atala, Anthony Nature Biotechnology, Vol. 32, Issue 8 https://doi.org/10.1038/nbt.2958	journal	August 2014
Multiphase design of autonomic self-healing thermoplastic elastomers Chen, Yulin; Kushner, Aaron M.; Williams, Gregory A. Nature Chemistry, Vol. 4, Issue 6 https://doi.org/10.1038/nchem.1314	journal	April 2012
Solvent-free, supersoft and superelastic bottlebrush melts and networks Daniel, William F. M.; Burdyńska, Joanna; Vatankhah-Varnoosfaderani, Mohammad Nature Materials, Vol. 15, Issue 2 https://doi.org/10.1038/nmat4508	journal	November 2015
3D printing of robotic soft actuators with programmable bioinspired architectures Schaffner, Manuel; Faber, Jakob A.; Pianegonda, Lucas Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03216-w	journal	February 2018
3D printable tough silicone double networks Wallin, Thomas J.; Simonsen, Leif-Erik; Pan, Wenyang Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17816-y	journal	August 2020
Bio-inspired pneumatic shape-morphing elastomers Siéfert, Emmanuel; Reyssat, Etienne; Bico, José Nature Materials, Vol. 18, Issue 1 https://doi.org/10.1038/s41563-018-0219-x	journal	November 2018
Printing ferromagnetic domains for untethered fast-transforming soft materials Kim, Yoonho; Yuk, Hyunwoo; Zhao, Ruike Nature, Vol. 558, Issue 7709 https://doi.org/10.1038/s41586-018-0185-0	journal	June 2018
Three-dimensional printing of hierarchical liquid-crystal-polymer structures Gantenbein, Silvan; Masania, Kunal; Woigk, Wilhelm Nature, Vol. 561, Issue 7722 https://doi.org/10.1038/s41586-018-0474-7	journal	September 2018
Voxelated soft matter via multimaterial multinozzle 3D printing Skylar-Scott, Mark A.; Mueller, Jochen; Visser, Claas W. Nature, Vol. 575, Issue 7782 https://doi.org/10.1038/s41586-019-1736-8	journal	November 2019
Molecular understanding for large deformations of soft bottlebrush polymer networks Cai, Li-Heng Soft Matter, Vol. 16, Issue 27 https://doi.org/10.1039/D0SM00759E	journal	January 2020
Soft biological materials and their impact on cell function Levental, Ilya; Georges, Penelope C.; Janmey, Paul A. Soft Matter, Vol. 3, Issue 3 https://doi.org/10.1039/b610522j	journal	January 2007
Hydrogel bioelectronics Yuk, Hyunwoo; Lu, Baoyang; Zhao, Xuanhe Chemical Society Reviews, Vol. 48, Issue 6 https://doi.org/10.1039/c8cs00595h	journal	January 2019
Highly stretchable hydrogels for UV curing based high-resolution multimaterial 3D printing Zhang, Biao; Li, Shiya; Hingorani, Hardik Journal of Materials Chemistry B, Vol. 6, Issue 20 https://doi.org/10.1039/c8tb00673c	journal	January 2018
Super-soft solvent-free bottlebrush elastomers for touch sensing Reynolds, Veronica G.; Mukherjee, Sanjoy; Xie, Renxuan Materials Horizons, Vol. 7, Issue 1 https://doi.org/10.1039/c9mh00951e	journal	January 2020
Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents Matyjaszewski, K.; Jakubowski, W.; Min, K. Proceedings of the National Academy of Sciences, Vol. 103, Issue 42 https://doi.org/10.1073/pnas.0602675103	journal	October 2006
Shape-shifting structured lattices via multimaterial 4D printing Boley, J. William; van Rees, Wim M.; Lissandrello, Charles Proceedings of the National Academy of Sciences, Vol. 116, Issue 42 https://doi.org/10.1073/pnas.1908806116	journal	October 2019
Viscoelastic shear properties of human vocal fold mucosa: Measurement methodology and empirical results Chan, Roger W.; Titze, Ingo R. The Journal of the Acoustical Society of America, Vol. 106, Issue 4 https://doi.org/10.1121/1.427947	journal	October 1999
Molecular structure of bottlebrush polymers in melts Paturej, Jarosław; Sheiko, Sergei S.; Panyukov, Sergey Science Advances, Vol. 2, Issue 11 https://doi.org/10.1126/sciadv.1601478	journal	November 2016
Grayscale digital light processing 3D printing for highly functionally graded materials Kuang, Xiao; Wu, Jiangtao; Chen, Kaijuan Science Advances, Vol. 5, Issue 5 https://doi.org/10.1126/sciadv.aav5790	journal	May 2019
Room temperature 3D printing of super-soft and solvent-free elastomers Xie, Renxuan; Mukherjee, Sanjoy; Levi, Adam E. Science Advances, Vol. 6, Issue 46 https://doi.org/10.1126/sciadv.abc6900	journal	November 2020
Continuous liquid interface production of 3D objects Tumbleston, J. R.; Shirvanyants, D.; Ermoshkin, N. Science, Vol. 347, Issue 6228 https://doi.org/10.1126/science.aaa2397	journal	March 2015
Advances in engineering hydrogels Zhang, Yu Shrike; Khademhosseini, Ali Science, Vol. 356, Issue 6337 https://doi.org/10.1126/science.aaf3627	journal	May 2017
3D nanofabrication by volumetric deposition and controlled shrinkage of patterned scaffolds Oran, Daniel; Rodriques, Samuel G.; Gao, Ruixuan Science, Vol. 362, Issue 6420 https://doi.org/10.1126/science.aau5119	journal	December 2018
Volumetric additive manufacturing via tomographic reconstruction Kelly, Brett E.; Bhattacharya, Indrasen; Heidari, Hossein Science, Vol. 363, Issue 6431 https://doi.org/10.1126/science.aau7114	journal	January 2019
3D bioprinting of collagen to rebuild components of the human heart Lee, A.; Hudson, A. R.; Shiwarski, D. J. Science, Vol. 365, Issue 6452 https://doi.org/10.1126/science.aav9051	journal	August 2019
Rapid, large-volume, thermally controlled 3D printing using a mobile liquid interface Walker, David A.; Hedrick, James L.; Mirkin, Chad A. Science, Vol. 366, Issue 6463 https://doi.org/10.1126/science.aax1562	journal	October 2019
Block Copolymer Thermodynamics: Theory and Experiment Bates, Frank S.; Fredrickson, Glenn H. Annual Review of Physical Chemistry, Vol. 41, Issue 1 https://doi.org/10.1146/annurev.pc.41.100190.002521	journal	October 1990
Polymer Chemistry Hiemenz, Paul C.; Lodge, Timothy P. CRC Press https://doi.org/10.1201/9781420018271	book	February 2007

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