Reversible actuation of thermoplastic multiblock copolymers with overlapping thermal transitions of crystalline and glassy domains
Abstract
Polymeric materials possessing specific features like programmability, high deformability, and easy processability are highly desirable for creating modern actuating systems. In this study, thermoplastic shape-memory polymer actuators obtained by combining crystallizable poly(ε-caprolactone) (PCL) and poly(3 S -isobutylmorpholin-2,5-dione) (PIBMD) segments in multiblock copolymers are described. We designed these materials according to our hypothesis that the confinement of glassy PIBMD domains present at the upper actuation temperature contribute to the stability of the actuator skeleton, especially at large programming strains. The copolymers have a phase-segregated morphology, indicated by the well-separated melting and glass transition temperatures for PIBMD and PCL, but possess a partially overlapping T m of PCL and T g of PIBMD in the temperature interval from 40 to 60 °C. Crystalline PIBMD hard domains act as strong physical netpoints in the PIBMD−PCL bulk material enabling high deformability (up to 2000%) and good elastic recoverability (up to 80% at 50 °C above T m,PCL ). In the programmed thermoplastic actuators a high content of crystallizable PCL actuation domains ensures pronounced thermoreversible shape changes upon repetitive cooling and heating. The programmed actuator skeleton, composed of PCL crystals present at the upper actuation temperature T high and the remaining glassy PIBMD domains, enabled oriented crystallization upon cooling. The actuation performance of PIBMD-PCL could be tailored by balancing the interplay between actuation and skeleton, but also by varying the quantity of crystalline PIBMD hard domains via the copolymer composition, the applied programming strain, and the choice of T high . The actuator with 17 mol% PIBMD showed the highest reversible elongation of 11.4% when programmed to a strain of 900% at 50 °C. It is anticipated that the presented thermoplastic actuator materials can be applied as modern compression textiles.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
Some thermoplastic polymers have been shown to feature the two-way SME under stress-free condition.
“However, some thermoplastic polymers, i.e., class (iii), have been shown to feature the two-way SME under stress-free condition [142-146].”
From Two-Way and Multiple-Way Shape Memory Polymers for Soft Robotics: An Overview (2020) · cites this paper as [146]
Cites
Examination of the secondary structure of proteins by deconvolved FTIR spectra
Byler, D. M., & Susi, H. (1986) · Biopolymers · doi:10.1002/bip.360250307 · Cited by 3,003 · see citing works
Soft Robotics: A Perspective—Current Trends and Prospects for the Future
Majidi, C. (2013) · Soft Robotics · doi:10.1089/soro.2013.0001 · Cited by 1,306 · see citing works
Stress–strain behavior of thermoplastic polyurethanes
Qi, H. J., & Boyce, M. C. (2004) · Mechanics of Materials · doi:10.1016/j.mechmat.2004.08.001 · Cited by 902 · see citing works
Dai, X., Zhang, Y., Gao, L., Bai, T., Wang, W., Cui, Y., & Liu, W. (2015) · Advanced Materials · doi:10.1002/adma.201500534 · Cited by 848 · see citing works
Crescenzi, V., Manzini, G., Calzolari, G., & Borri, C. (1972) · European Polymer Journal · doi:10.1016/0014-3057(72)90109-7 · Cited by 751 · see citing works
Reversible bidirectional shape-memory polymers
Behl, M., Kratz, K., Zotzmann, J., Nöchel, U., & Lendlein, A. (2013) · Advanced Materials · doi:10.1002/adma.201300880 · Cited by 496 · see citing works
Self-citationInfrared Studies of Segmented Polyurethan Elastomers. I. Hydrogen Bonding
Seymour, R. W., Estes, G. M., & Cooper, S. L. (1970) · Macromolecules · doi:10.1021/ma60017a021 · Cited by 481 · see citing works
3D printed reversible shape changing components with stimuli responsive materials
Mao, Y., Ding, Z., Yuan, C., Ai, S., Isakov, M., Wu, J., Wang, T., Dunn, M. L., & Qi, H. J. (2016) · Scientific Reports · doi:10.1038/srep24761 · Cited by 348 · see citing works
Temperature-memory polymer actuators
Behl, M., Kratz, K., Noechel, U., Sauter, T., & Lendlein, A. (2013) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1301895110 · Cited by 313 · see citing works
Self-citationThe structure, microphase-separated morphology, and property of polyurethanes and polyureas
He, Y., Xie, D., & Zhang, X. (2014) · Journal of Materials Science · doi:10.1007/s10853-014-8458-y · Cited by 291 · see citing works
Flexible and Stretchable Strain Sensing Actuator for Wearable Soft Robotic Applications
Yeo, J. C., Yap, H. K., Xi, W., Wang, Z., Yeow, C., & Lim, C. T. (2016) · Advanced Materials Technologies · doi:10.1002/admt.201600018 · Cited by 254 · see citing works
Shapeshifting: Reversible shape memory in semicrystalline elastomers
Zhou, J., Turner, S. A., Brosnan, S. M., Li, Q., Carrillo, J.-M. Y., Nykypanchuk, D., Gang, O., Ashby, V. S., Dobrynin, A. V., & Sheiko, S. S. (2014) · Macromolecules · doi:10.1021/ma4023185 · Cited by 209 · see citing works
Two-way shape memory effect in polymer laminates
Chen, S., Hu, J., Zhuo, H., & Zhu, Y. (2008) · Materials Letters · doi:10.1016/j.matlet.2008.05.073 · Cited by 158 · see citing works
Wang, K., Jia, Y.-G., & Zhu, X. X. (2017) · Macromolecules · doi:10.1021/acs.macromol.7b01815 · Cited by 134 · see citing works
Biomimetic Soft Actuator: Design, Modeling, Control, and Applications
Choi, H. R., Jung, K., Ryew, S. M., et al. (2005) · IEEE/ASME Transactions on Mechatronics · doi:10.1109/tmech.2005.856108 · Cited by 115 · see citing works
Biodegradable Multiblock Copolymers Based on Oligodepsipeptides with Shape‐Memory Properties
Feng, Y., Behl, M., Kelch, S., & Lendlein, A. (2009) · Macromolecular Bioscience · doi:10.1002/mabi.200800199 · Cited by 114 · see citing works
Self-citationBidirectional actuation of a thermoplastic polyurethane elastomer
Bothe, M., & Pretsch, T. (2013) · Journal of Materials Chemistry A · doi:10.1039/c3ta13414h · Cited by 112 · see citing works
Lu, L., & Li, G. (2016) · ACS Applied Materials & Interfaces · doi:10.1021/acsami.6b04105 · Cited by 102 · see citing works
Polyolefin thermoplastics for multiple shape and reversible shape memory
Gao, Y., Liu, W., & Zhu, S. (2017) · ACS Applied Materials & Interfaces · doi:10.1021/acsami.6b14728 · Cited by 99 · see citing works
Peng, Q., Wei, H., Qin, Y., Lin, Z., Zhao, X., Xu, F., Leng, J., He, X., Cao, A., & Li, Y. (2016) · Nanoscale · doi:10.1039/c6nr06515e · Cited by 98 · see citing works
Biodegradable Polydepsipeptides
Feng, Y., & Guo, J. (2009) · International Journal of Molecular Sciences · doi:10.3390/ijms10020589 · Cited by 96 · see citing works
Zhu, P., Dong, X., & Wang, D. (2017) · Macromolecules · doi:10.1021/acs.macromol.6b02747 · Cited by 95 · see citing works
Saatchi, M., Behl, M., Nöchel, U., & Lendlein, A. (2015) · Macromolecular Rapid Communications · doi:10.1002/marc.201400729 · Cited by 81 · see citing works
Self-citationReversible Bidirectional Shape Memory Effect in Polyurethanes through Molecular Flipping
Biswas, A., Aswal, V. K., Sastry, P. U., Rana, D., & Maiti, P. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b00536 · Cited by 78 · see citing works
Progress in Depsipeptide‐Based Biomaterials
Feng, Y., Lu, J. B., Behl, M., & Lendlein, A. (2010) · Macromolecular Bioscience · doi:10.1002/mabi.201000076 · Cited by 77 · see citing works
Self-citationCrystallization under Strain and Resultant Orientation of Poly(ε-caprolactone) in Miscible Blends
Zhao, Y., Keroack, D., & Prud'homme, R. E. (1999) · Macromolecules · doi:10.1021/ma981416o · Cited by 75 · see citing works
Asaka, K., & Okuzaki, H. (2014) · Springer eBooks · doi:10.1007/978-4-431-54767-9 · Cited by 73 · see citing works
Yang, H., Liu, D., Ju, J., Li, J., Wang, Z., Yan, G., Ji, Y., Zhang, W., Sun, G., & Li, L. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b01945 · Cited by 51 · see citing works
Zhang, C., Hu, J., Li, X., Wu, Y., & Han, J. (2014) · The Journal of Physical Chemistry A · doi:10.1021/jp508817v · Cited by 49 · see citing works
Matsumiya, Y., Watanabe, H., Takano, A., & Takahashi, Y. (2013) · Macromolecules · doi:10.1021/ma3026404 · Cited by 47 · see citing works
Huang, M., Zheng, L., Wang, L., Dong, X., Gao, X., Li, C., & Wang, D. (2017) · ACS Applied Materials & Interfaces · doi:10.1021/acsami.7b08403 · Cited by 42 · see citing works
Hidden Thermoreversible Actuation Behavior of Nafion and Its Morphological Origin
Xie, T., Li, J., & Zhao, Q. (2014) · Macromolecules · doi:10.1021/ma402203q · Cited by 39 · see citing works
Segmented poly(urethane‐urea) elastomers based on polycaprolactone: Structure and properties
May-Hernández, L. H., Hernández‐Sánchez, F., Ribelles, J. L. G., et al. (2010) · Journal of Applied Polymer Science · doi:10.1002/app.32929 · Cited by 36 · see citing works
On the Orientation-Induced Crystallization of Polymers
Nitta, K. (2016) · Polymers · doi:10.3390/polym8060229 · Cited by 34 · see citing works
Thermally-triggered free-standing shape-memory actuators
Belmonte, A., Lama, G. C., Gentile, G., Cerruti, P., Ambrogi, V., Fernández‐Francos, X., & la Flor, S. D. (2017) · European Polymer Journal · doi:10.1016/j.eurpolymj.2017.10.006 · Cited by 34 · see citing works
Han, J., Lai, S., & Chiu, Y. T. (2018) · Polymers for Advanced Technologies · doi:10.1002/pat.4309 · Cited by 34 · see citing works
Noncontinuously Responding Polymeric Actuators
Farhan, M., Rudolph, T., Nöchel, U., Yan, W., Kratz, K. L., & Lendlein, A. (2017) · ACS Applied Materials & Interfaces · doi:10.1021/acsami.7b11316 · Cited by 27 · see citing works
Self-citationNoncontinuously Responding Polymeric Actuators
Rudolph, T., Farhan, M., Noechel, U., et al. (2018) · Cited by 17 · see citing works
Self-citationFernández–d’Arlas, B., Corcuera, M. Á., Runt, J. P., et al. (2013) · Polymer International · doi:10.1002/pi.4669 · Cited by 15 · see citing works
Wang, L., Wang, J., Yang, B., et al. (2013) · Colloid & Polymer Science · doi:10.1007/s00396-012-2887-4 · Cited by 12 · see citing works
Wan, Y. P., Fang, L., Weigel, T., Behl, M., Kratz, K. L., & Lendlein, A. (2016) · Polymers for Advanced Technologies · doi:10.1002/pat.3953 · Cited by 7 · see citing works
Self-citation
Flagged first, then by citations
Cited by
Sorted by citations
Two-Way and Multiple-Way Shape Memory Polymers for Soft Robotics: An Overview
Scalet, G. (2020) · Actuators · doi:10.3390/act9010010 · Cited by 209 · see citing works
Scalet, G., Pandini, S., Messori, M., Toselli, M., & Auricchio, F. (2018) · Polymer · doi:10.1016/j.polymer.2018.10.027 · Cited by 38 · see citing works
Izraylit, V., Gould, O. E. C., Rudolph, T., Kratz, K., & Lendlein, A. (2020) · Biomacromolecules · doi:10.1021/acs.biomac.9b01279 · Cited by 25 · see citing works
Self-citation
- Authors
- Yan, W., Rudolph, T., Noechel, U., Gould, O., Behl, M., Kratz, K., & Lendlein, A.
- Affiliations
- Institute of Biomaterial Science and Berlin-Brandenburg Center for Regenerative Therapies, Helmholtz-Zentrum Geesthacht, Kantstr. 55, 14513 Teltow, Germany
- Helmholtz-Zentrum Hereon (DE)
- Tianjin University (CN)
- Corresponding author
- Lendlein, Andreas
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2018-06-12
- Volume
- 51
- Issue
- 12
- Pages
- 4624-4632
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2808077433
- Cited by
- 29
- References
- 41
- Citations by year
- 2026: 1 · 2025: 1 · 2024: 5 · 2023: 3 · 2022: 3 · 2021: 3 · 2020: 4 · 2019: 7 · 2018: 2
- FWCI
- 2.56
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- publish.UP (University of Potsdam) (submittedVersion)
- Funders
- Helmholtz-Gemeinschaft (VH-GS-503)
- Ministry of Science and Technology of the People's Republic of China (2008DFA51170)
- Bundesministerium fuer Bildung und Forschung (031A095, 315496)
- Topics
- Physical Sciences › Engineering › Mechanical Engineering › Advanced Materials and Mechanics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer composites and self-healing
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Keywords
- multiblock copolymers, polycaprolactone, oriented crystallization
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
