Abstract
In this work, we have prepared films based on cellulose nanofibers (CNFs) that mimic plant responsiveness to water by shape-changing. Film twisting was achieved by creating an asymmetrical expansion through a gradient of carboxylate groups within the CNF film thickness. We present the characterization of pristine and modified CNFs, and their swelling and mechanical performances when conditioned into films. The immersion in water and organic solvents (isopropanol, ethanol, DMSO, acetonitrile, and cyclohexane) allowed controlling the asymmetrical expansion. Hence, film twisting is triggered when immersed in water and their shape recoveries were accomplished by dipping them in organic solvents. We investigated the main physicochemical interactions between the different CNFs and solvents governing film expansion. This work leaves the door open for the design of biomimetic cellulose-based materials for soft robotics, building materials, and electronic applications.
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The datasets generated during the current study are available from the corresponding author on reasonable request.
References
Abitbol T, Kloser E, Gray DG (2013) Estimation of the surface sulfur content of cellulose nanocrystals prepared by sulfuric acid hydrolysis. Cellulose 20:785–794. https://doi.org/10.1007/s10570-013-9871-0
Baati R, Magnin A, Boufi S (2017) High solid content production of nanofibrillar cellulose via continuous extrusion. ACS Sustain Chem Eng 5:2350–2359. https://doi.org/10.1021/acssuschemeng.6b02673
Barton AFM (1991) Handbook of solubility parameters and other cohesion parameters. pp 277–284
Beck S, Méthot M, Bouchard J (2015) General procedure for determining cellulose nanocrystal sulfate half-ester content by conductometric titration. Cellulose 22:101–116. https://doi.org/10.1007/s10570-014-0513-y
Benítez AJ, Walther A (2017) Cellulose nanofibril nanopapers and bioinspired nanocomposites: a review to understand the mechanical property space. J Mater Chem A 5:16003–16024. https://doi.org/10.1039/c7ta02006f
Benítez AJ, Torres-Rendon J, Poutanen M, Walther A (2013) Humidity and multiscale structure govern mechanical properties and deformation modes in films of native cellulose nanofibrils. Biomacromolecules 14:4497–4506. https://doi.org/10.1021/bm401451m
Boufi S, Chaker A (2016) Easy production of cellulose nanofibrils from corn stalk by a conventional high speed blender. Ind Crops Prod 93:39–47. https://doi.org/10.1016/j.indcrop.2016.05.030
Burgert I, Keplinger T, Cabane E et al (2016) Biomaterial wood: wood-based and bioinspired materials. Elsevier, Amsterdam
Capadona JR, Shanmuganathan K, Tyler DJ et al (2008) Stimuli-responsive polymer nanocomposites inspired by the sea cucumber dermis. Science 319:1370–1374. https://doi.org/10.1126/science.1153307
Chemin M, Beaumal B, Cathala B, Villares A (2020) Ph-responsive properties of asymmetric nanopapers of nanofibrillated cellulose. Nanomaterials 10:1–14. https://doi.org/10.3390/nano10071380
Chen Y, Wan J, Dong X, Ma Y (2013) Fiber properties of eucalyptus kraft pulp with different carboxyl group contents. Cellulose 206 20:2839–2846. https://doi.org/10.1007/S10570-013-0055-8
Chen W, Sun B, Biehl P, Zhang K (2022) Cellulose-based soft actuators. Macromol Mater Eng. https://doi.org/10.1002/mame.202200072
da Silva Perez D, Montanari S, Vignon MR (2003) TEMPO-mediated oxidation of cellulose III. Biomacromolecules 4:1417–1425. https://doi.org/10.1021/bm034144s
Dawson C, Vincent J, Rocca A (1997) How pine cone open. Nature 390:668
Duan J, Liang X, Zhu K et al (2017) Bilayer hydrogel actuators with tight interfacial adhesion fully constructed from natural polysaccharides. Soft Matter 13:345–354. https://doi.org/10.1039/c6sm02089e
Duchemin B (2022) The sustainability of phytomass-derived materials: thermodynamical aspects, life cycle analysis and research perspectives. Green Chem 24:2653–2679. https://doi.org/10.1039/d1gc03262c
Duigou A, Le, Requile S, Beaugrand J et al (2017) Natural fibres actuators for smart bio-inspired hygromorph biocomposites. Smart Mater Struct 26:125009. https://doi.org/10.1088/1361-665X/AA9410
El Seoud OA, Fidale LC, Ruiz N et al (2008) Cellulose swelling by protic solvents: which properties of the biopolymer and the solvent matter? Cellulose 15:371–392. https://doi.org/10.1007/s10570-007-9189-x
Erb RM, Sander JS, Grisch R, Studart AR (2013) Self-shaping composites with programmable bioinspired microstructures. Nat Commun 4:1–8. https://doi.org/10.1038/ncomms2666
Fält S, Wågberg L, Vesterlind EL (2003) Swelling of model films of cellulose having different charge densities and comparison to the swelling behavior of corresponding fibers. Langmuir 19:7895–7903. https://doi.org/10.1021/la026984i
Faruk O, Bledzki AK, Fink HP, Sain M (2012) Biocomposites reinforced with natural fibers: 2000–2010. Prog Polym Sci 37:1552–1596. https://doi.org/10.1016/j.progpolymsci.2012.04.003
Fidale LC, Ruiz N, Heinze T, El Seoud OA (2008) Cellulose swelling by aprotic and protic solvents: what are the similarities and differences? Macromol Chem Phys 209:1240–1254. https://doi.org/10.1002/macp.200800021
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/S10570-013-0030-4
French AD, Santiago Cintrón M (2013) Cellulose polymorphy, crystallite size, and the Segal Crystallinity Index. Cellulose 20:583–588. https://doi.org/10.1007/s10570-012-9833-y
Ganewatta MS, Wang Z, Tang C (2021) Chemical syntheses of bioinspired and biomimetic polymers toward biobased materials. Nat Rev Chem 2021 511 5:753–772. https://doi.org/10.1038/s41570-021-00325-x
Huber T, Müssig J, Curnow O et al (2011) A critical review of all-cellulose composites. J Mater Sci 47:1171–1186. https://doi.org/10.1007/S10853-011-5774-3
Im W, Lee S, Rajabi Abhari A et al (2018) Optimization of carboxymethylation reaction as a pretreatment for production of cellulose nanofibrils. Cellulose 25:3873–3883. https://doi.org/10.1007/s10570-018-1853-9
Ju X, Bowden M, Brown EE, Zhang X (2015) An improved X-ray diffraction method for cellulose crystallinity measurement. Carbohydr Polym 123:476–481. https://doi.org/10.1016/j.carbpol.2014.12.071
Kono H, Oshima K, Hashimoto H et al (2016) NMR characterization of sodium carboxymethyl cellulose: substituent distribution and mole fraction of monomers in the polymer chains. Carbohydr Polym 146:1–9. https://doi.org/10.1016/j.carbpol.2016.03.021
Kuang Y, Chen C, Cheng J et al (2019) Selectively aligned cellulose nanofibers towards high-performance soft actuators. Extrem Mech Lett 29:100463. https://doi.org/10.1016/j.eml.2019.100463
Liang Y, Liu C, Xiu H et al (2020) Effect of 3D printing parameters on self-driven deformation characteristics of intelligent hydrogel actuators. ChemistrySelect 5:10367–10373. https://doi.org/10.1002/slct.202002424
Markstedt K, Håkansson K, Toriz G, Gatenholm P (2019) Materials from trees assembled by 3D printing: wood tissue beyond nature limits. Appl Mater Today 15:280–285. https://doi.org/10.1016/j.apmt.2019.02.005
Mayeen A, Shaji LK, Nair AK, Kalarikkal N (2018) Morphological characterization of nanomaterials. Charact Nanomater Adv Key Technol. https://doi.org/10.1016/B978-0-08-101973-3.00012-2
Mohkami M, Talaeipour M (2011) Investigation of the chemical structure of carboxylated and carboxymethylated fibers from waste paper via XRD and FTIR analysis. BioResources 6:1988–2003
Mokhena TC, Sadiku ER, Mochane MJ et al (2021) Mechanical properties of cellulose nanofibril papers and their bionanocomposites: a review. Carbohydr Polym 273:118507. https://doi.org/10.1016/j.carbpol.2021.118507
Mulakkal MC, Trask RS, Ting VP, Seddon AM (2018) Responsive cellulose-hydrogel composite ink for 4D printing. Mater Des 160:108–118. https://doi.org/10.1016/j.matdes.2018.09.009
Oh SY, Dong IY, Shin Y et al (2005) Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy. Carbohydr Res 340:2376–2391. https://doi.org/10.1016/j.carres.2005.08.007
Peng N, Huang D, Gong C et al (2020) Controlled arrangement of Nanocellulose in Polymeric Matrix: from reinforcement to functionality. ACS Nano 14:16169–16179. https://doi.org/10.1021/acsnano.0c08906
Reid MS, Villalobos M, Cranston ED (2016) Cellulose nanocrystal interactions probed by thin film swelling to predict dispersibility. Nanoscale 8:12247–12257. https://doi.org/10.1039/c6nr01737a
Saito T, Isogai A (2004) TEMPO-Mediated oxidation of native cellulose. The Effect of Oxidation Conditions on Chemical and Crystal Structures of the water-insoluble fractions. Biomacromolecules 5:1983–1989. https://doi.org/10.1021/bm0497769
Saito T, Shibata I, Isogai A et al (2005) Distribution of carboxylate groups introduced into cotton linters by the TEMPO-mediated oxidation. Carbohydr Polym 61:414–419. https://doi.org/10.1016/j.carbpol.2005.05.014
Schwanninger M, Rodrigues JC, Pereira H, Hinterstoisser B (2004) Effects of short-time vibratory ball milling on the shape of FT-IR spectra of wood and cellulose. Vib Spectrosc 36:23–40. https://doi.org/10.1016/j.vibspec.2004.02.003
Segal L, Creely JJ, Martin AE, Conrad J CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-Ray diffractometer. Text Res J 29:786–794. https://doi.org/10.1177/004051755902901003
Smallwood IM (2012) Handbook of organic solvent properties. pp 1–306. https://doi.org/10.1016/C2009-0-23646-4
Srinivasan AV, Haritos GK, Hedberg FL (1991) Biomimetics: advancing man-made materials through guidance from nature. Appl Mech Rev 44:463–482. https://doi.org/10.1115/1.3119489
Venkatram S, Kim C, Chandrasekaran A, Ramprasad R (2019) Critical assessment of the hildebrand and hansen solubility parameters for polymers. J Chem Inf Model. https://doi.org/10.1021/acs.jcim.9b00656
Wågberg L, Decher G, Norgren M et al (2008) The build-up of polyelectrolyte multilayers of microfibrillated cellulose and cationic polyelectrolytes. Langmuir 24:784–795. https://doi.org/10.1021/la702481v
Wang M, Tian X, Ras RHA, Ikkala O (2015) Sensitive humidity-driven reversible and bidirectional bending of nanocellulose thin films as bio-inspired actuation. Adv Mater Interfaces 2:1500080. https://doi.org/10.1002/admi.201500080
Wang X, Huang H, Liu H et al (2019) Multi-Responsive Bilayer Hydrogel Actuators with programmable and precisely tunable motions. Macromol Chem Phys 220:1–8. https://doi.org/10.1002/macp.201800562
Wang L, Li K, Copenhaver K et al (2021) Review on nonconventional fibrillation methods of producing cellulose nanofibrils and their applications. Biomacromolecules 22:4037–4059. https://doi.org/10.1021/acs.biomac.1C00640
Wei J, Jia S, Guan J et al (2021) Robust and highly sensitive cellulose nanofiber-based humidity actuators. ACS Appl Mater Interfaces 13:54417–54427. https://doi.org/10.1021/acsami.1c17894
Yang L, Cui J, Zhang L et al (2021) A moisture-driven actuator based on polydopamine-modified MXene/bacterial cellulose nanofiber composite film. Adv Funct Mater 31:1–11. https://doi.org/10.1002/adfm.202101378
Zhang L, Chizhik S, Wen Y, Naumov P (2016) Directed motility of hygroresponsive biomimetic actuators. Adv Funct Mater 26:1040–1053. https://doi.org/10.1002/adfm.201503922
Zhang X, Yu Y, Jiang Z, Wang H (2016b) Influence of thickness and moisture content on the mechanical properties of microfibrillated cellulose (MFC) films. Wood Res 61:851–860
Zhao Q, Liang Y, Ren L et al (2018) Design and fabrication of nanofibrillated cellulose-containing bilayer hydrogel actuators with temperature and near infrared laser responses. J Mater Chem B 6:1260–1271. https://doi.org/10.1039/c7tb02853a
Zhao Q, Chang Y, Yu Z et al (2020) Bionic intelligent soft actuators: high-strength gradient intelligent hydrogels with diverse controllable deformations and movements. J Mater Chem B 8:9362–9373. https://doi.org/10.1039/d0tb01927e
Zhou S, Zhou S, Zhou Q et al (2020) Design and preparation of 3D printing intelligent poly N,N-dimethylacrylamide hydrogel actuators. E-Polymers 20:273–281. https://doi.org/10.1515/epoly-2020-0033
Acknowledgments
The authors gratefully thank the financial support of Région Pays de la Loire and Transform Division from the French National Research Institute for Agriculture, Food and Environment. The authors acknowledge the Bioresources, Imaging, Biochemistry, and Structure (BIBS) platform of INRAE for the access to microscopy facilities (Bruno Novales) and X-ray diffraction (Bruno Pontoire). Anne-Laure Reguerre is acknowledged for the excellent technical support for image acquisition and treatment. We gratefully acknowledge Borregaard for kindly supplying the cellulose nanofibers.
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The authors gratefully thank the financial support of Région Pays de la Loire and Transform Division from the French National Research Institute for Agriculture, Food and Environment.
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LL: Conceptualization, investigation, discussion, writing—original draft, writing—review and editing. CM: Discussion, writing—review and editing. DL: Investigation, discussion, writing—review and editing. BC: Discussion, Writing—review and editing. AV: Conceptualization, Investigation, discussion, funding acquisition, project administration, supervision, writing—review and editing. All authors have read and agreed to the published version of the manuscript.
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Lopes da Costa, L., Moreau, C., Lourdin, D. et al. Shape-recovery in organic solvents of water-responsive cellulose nanofiber actuators. Cellulose 30, 5811–5824 (2023). https://doi.org/10.1007/s10570-023-05230-8
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DOI: https://doi.org/10.1007/s10570-023-05230-8