Determination of Young’s Modulus for Nanofibrillated Cellulose Multilayer Thin Films Using Buckling Mechanics
- Emily D. Cranston ,
- Mohamed Eita ,
- Erik Johansson ,
- Julia Netrval ,
- Michaela Salajková ,
- Hans Arwin , and
- Lars Wågberg
Abstract

The Young’s modulus of multilayer films containing nanofibrillated cellulose (NFC) and polyethyleneimine (PEI) was determined using the strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) technique. (1) Multilayer films were built up on polydimethylsiloxane substrates using electrostatic layer-by-layer assembly. At 50% relative humidity, SIEBIMM gave a constant Young’s modulus of 1.5 ± 0.2 GPa for 35−75 nm thick films. Conversely, in vacuum, the Young’s modulus was 10 times larger, at 17.2 ± 1.2 GPa. A slight decrease in buckling wavelength with increasing strain was observed by scanning electron microscopy with in situ compression, and above 10% strain, extensive cracking parallel to the compressive direction occurred. We conclude that whereas PEI acts as a “glue” to hold multiple layers of NFC together, it prevents full development of hydrogen bonding and specific fibril−fibril interactions, and at high humidity, its hygroscopic nature decreases the elastic modulus when compared with pure NFC films.
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- Marcos Mariano Alain Dufresne . Nanocellulose: Common Strategies for Processing of Nanocomposites. 2017,,, 203-225. https://doi.org/10.1021/bk-2017-1251.ch011
- Hongli Zhu, Wei Luo, Peter N. Ciesielski, Zhiqiang Fang, J. Y. Zhu, Gunnar Henriksson, Michael E. Himmel, and Liangbing Hu . Wood-Derived Materials for Green Electronics, Biological Devices, and Energy Applications. Chemical Reviews 2016, 116 (16) , 9305-9374. https://doi.org/10.1021/acs.chemrev.6b00225
- Giulia L. Ferretti, Manuela Nania, Omar K. Matar, and João T. Cabral . Wrinkling Measurement of the Mechanical Properties of Drying Salt Thin Films. Langmuir 2016, 32 (9) , 2199-2207. https://doi.org/10.1021/acs.langmuir.5b04488
- Alexis Wells Carpenter, Charles-François de Lannoy, and Mark R. Wiesner . Cellulose Nanomaterials in Water Treatment Technologies. Environmental Science & Technology 2015, 49 (9) , 5277-5287. https://doi.org/10.1021/es506351r
- Jiaqi Zhu, Wenxin Cao, Mingli Yue, Ying Hou, Jiecai Han, and Ming Yang . Strong and Stiff Aramid Nanofiber/Carbon Nanotube Nanocomposites. ACS Nano 2015, 9 (3) , 2489-2501. https://doi.org/10.1021/nn504927e
- Houssine Sehaqui, María Elena Gálvez, Viola Becatinni, Yi cheng Ng, Aldo Steinfeld, Tanja Zimmermann, and Philippe Tingaut . Fast and Reversible Direct CO2 Capture from Air onto All-Polymer Nanofibrillated Cellulose—Polyethylenimine Foams. Environmental Science & Technology 2015, 49 (5) , 3167-3174. https://doi.org/10.1021/es504396v
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- Jiangqi Zhao, Canhui Lu, Xu He, Xiaofang Zhang, Wei Zhang, and Ximu Zhang . Polyethylenimine-Grafted Cellulose Nanofibril Aerogels as Versatile Vehicles for Drug Delivery. ACS Applied Materials & Interfaces 2015, 7 (4) , 2607-2615. https://doi.org/10.1021/am507601m
- Xuan Yang and Emily D. Cranston . Chemically Cross-Linked Cellulose Nanocrystal Aerogels with Shape Recovery and Superabsorbent Properties. Chemistry of Materials 2014, 26 (20) , 6016-6025. https://doi.org/10.1021/cm502873c
- Emil Gustafsson, Erik Johansson, Lars Wågberg, and Torbjörn Pettersson . Direct Adhesive Measurements between Wood Biopolymer Model Surfaces. Biomacromolecules 2012, 13 (10) , 3046-3053. https://doi.org/10.1021/bm300762e
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- P. Samyn and M.-P. Laborie , A. P. Mathew , A. Airoudj, H. Haidara, and V. Roucoules . Metastable Patterning of Plasma Nanocomposite Films by Incorporating Cellulose Nanowhiskers. Langmuir 2012, 28 (2) , 1427-1438. https://doi.org/10.1021/la202503h
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- Lars Wågberg, Johan Erlandsson. The Use of Layer‐by‐Layer Self‐Assembly and Nanocellulose to Prepare Advanced Functional Materials. Advanced Materials 2021, 33 (28) , 2001474. https://doi.org/10.1002/adma.202001474
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- Young-Chul Lee, Ju-Young Moon. Bionanotechnology in Environment. 2020,,, 219-234. https://doi.org/10.1007/978-981-15-1293-3_12
- Panpan Li, Juho Antti Sirviö, Shu Hong, Ari Ämmälä, Henrikki Liimatainen. Preparation of flame-retardant lignin-containing wood nanofibers using a high-consistency mechano-chemical pretreatment. Chemical Engineering Journal 2019, 375 , 122050. https://doi.org/10.1016/j.cej.2019.122050
- Yadong Wu, Fang Wang, Yudong Huang. Facile fabrication and performance comparison of aramid‐nanofiber membrane formed by water or ethanol. Polymer Composites 2019, 40 (6) , 2534-2538. https://doi.org/10.1002/pc.25157
- Mitchell L. Rencheck, Ricardo Rodriguez, Nolan A. Miller, Chelsea S. Davis. A buckling mechanics approach to elastic modulus determination of glassy polymer films. Journal of Polymer Science Part B: Polymer Physics 2019, 57 (1) , 15-20. https://doi.org/10.1002/polb.24755
- Xiao Zhang, Jing Zhao, Chad R. Snyder, Abdullah Al‐Enizi, Ahmed Eltazahry, David S. Simmons, Alamgir Karim. Structure, nanomechanics, and dynamics of dispersed surfactant‐free clay nanocomposite films. Polymer Engineering & Science 2018, 58 (8) , 1285-1295. https://doi.org/10.1002/pen.24693
- Patrick Laurén, Heli Paukkonen, Tiina Lipiäinen, Yujiao Dong, Timo Oksanen, Heikki Räikkönen, Henrik Ehlers, Päivi Laaksonen, Marjo Yliperttula, Timo Laaksonen. Pectin and Mucin Enhance the Bioadhesion of Drug Loaded Nanofibrillated Cellulose Films. Pharmaceutical Research 2018, 35 (7) https://doi.org/10.1007/s11095-018-2428-z
- Marcus Vinícius Tavares da Costa, Cristian Neagu, Pierre Fayet, Urban Wiklund, Hu Li, Klaus Leifer, E. Kristofer Gamstedt. Comparison of test methods estimating the stiffness of ultrathin coatings. Journal of Coatings Technology and Research 2018, 15 (4) , 743-752. https://doi.org/10.1007/s11998-018-0085-0
- Benjamin P. Wilson, Kirsi Yliniemi, Marie Gestranius, Minna Hakalahti, Matti Putkonen, Mari Lundström, Maarit Karppinen, Tekla Tammelin, Eero Kontturi. Structural distinction due to deposition method in ultrathin films of cellulose nanofibres. Cellulose 2018, 25 (3) , 1715-1724. https://doi.org/10.1007/s10570-018-1665-y
- Da Chen, Lei Yang, Wenhua Yu, Maozeng Wu, Wei Wang, Hongfei Wang. Micro-Electromechanical Acoustic Resonator Coated with Polyethyleneimine Nanofibers for the Detection of Formaldehyde Vapor. Micromachines 2018, 9 (2) , 62. https://doi.org/10.3390/mi9020062
- Jun Chen, Veronika Kozlovskaya, Daniëlle Pretorius, Eugenia Kharlampieva. Multilayer Assemblies of Biopolymers. 2018,,, 57-106. https://doi.org/10.1002/9781119156253.ch3
- Nursel Pekel Bayramgil. Grafting of Hydrophilic Monomers Onto Cellulosic Polymers for Medical Applications. 2018,,, 81-114. https://doi.org/10.1016/B978-0-12-810462-0.00003-X
- Sandra A. Nascimento, Camila A. Rezende. Combined approaches to obtain cellulose nanocrystals, nanofibrils and fermentable sugars from elephant grass. Carbohydrate Polymers 2018, 180 , 38-45. https://doi.org/10.1016/j.carbpol.2017.09.099
- E. Johan Foster, Robert J. Moon, Umesh P. Agarwal, Michael J. Bortner, Julien Bras, Sandra Camarero-Espinosa, Kathleen J. Chan, Martin J. D. Clift, Emily D. Cranston, Stephen J. Eichhorn, Douglas M. Fox, Wadood Y. Hamad, Laurent Heux, Bruno Jean, Matthew Korey, World Nieh, Kimberly J. Ong, Michael S. Reid, Scott Renneckar, Rose Roberts, Jo Anne Shatkin, John Simonsen, Kelly Stinson-Bagby, Nandula Wanasekara, Jeff Youngblood. Current characterization methods for cellulose nanomaterials. Chemical Society Reviews 2018, 47 (8) , 2609-2679. https://doi.org/10.1039/C6CS00895J
- Wadood Y. Hamad. Cellulose Nanocrystals and Nanofibrils in Advanced Applications. 2017,,, 799-832. https://doi.org/10.1002/9783527689972.ch24
- Huanqing Ma, Shujun Wang, Fanbin Meng, Xingyu Xu, Xianliang Huo. A hydrazone-carboxyl ligand-linked cellulose nanocrystal aerogel with high elasticity and fast oil/water separation. Cellulose 2017, 24 (2) , 797-809. https://doi.org/10.1007/s10570-016-1132-6
- Urooj Gill, Travis Sutherland, Sebastian Himbert, Yujie Zhu, Maikel C. Rheinstädter, Emily D. Cranston, Jose M. Moran-Mirabal. Beyond buckling: humidity-independent measurement of the mechanical properties of green nanobiocomposite films. Nanoscale 2017, 9 (23) , 7781-7790. https://doi.org/10.1039/C7NR00251C
- Jing Lyu, Lehao Liu, Xing Zhao, Yudong Shang, Tingkai Zhao, Tiehu Li. Facile Fabrication of Multifunctional Aramid Nanofiber Films by Spin Coating. Journal of Materials Engineering and Performance 2016, 25 (11) , 4757-4763. https://doi.org/10.1007/s11665-016-2350-7
- Viviane da Costa Correia, Valdemir dos Santos, Mohini Sain, Sergio Francisco Santos, Alcides Lopes Leão, Holmer Savastano Junior. Grinding process for the production of nanofibrillated cellulose based on unbleached and bleached bamboo organosolv pulp. Cellulose 2016, 23 (5) , 2971-2987. https://doi.org/10.1007/s10570-016-0996-9
- Benjamin Megevand, Sébastien Pruvost, Luanda C. Lins, Sébastien Livi, Jean-François Gérard, Jannick Duchet-Rumeau. Probing nanomechanical properties with AFM to understand the structure and behavior of polymer blends compatibilized with ionic liquids. RSC Advances 2016, 6 (98) , 96421-96430. https://doi.org/10.1039/C6RA18492H
- Claudia D. Simão, Juan S. Reparaz, Markus R. Wagner, Bartlomiej Graczykowski, Martin Kreuzer, Yasser B. Ruiz-Blanco, Yamila García, Jani-Markus Malho, Alejandro R. Goñi, Jouni Ahopelto, Clivia M. Sotomayor Torres. Optical and mechanical properties of nanofibrillated cellulose: Toward a robust platform for next-generation green technologies. Carbohydrate Polymers 2015, 126 , 40-46. https://doi.org/10.1016/j.carbpol.2015.03.032
- Ming Yang, Keqin Cao, Bongjun Yeom, MD Thouless, Anthony Waas, Ellen M Arruda, Nicholas A Kotov. Aramid nanofiber-reinforced transparent nanocomposites. Journal of Composite Materials 2015, 49 (15) , 1873-1879. https://doi.org/10.1177/0021998315579230
- Archim Wolfberger, Andreas Petritz, Alexander Fian, Jakob Herka, Volker Schmidt, Barbara Stadlober, Rupert Kargl, Stefan Spirk, Thomas Griesser. Photolithographic patterning of cellulose: a versatile dual-tone photoresist for advanced applications. Cellulose 2015, 22 (1) , 717-727. https://doi.org/10.1007/s10570-014-0471-4
- Kaiwen Liang, Sheldon Shi, Ge Wang. Effect of Impregnated Inorganic Nanoparticles on the Properties of the Kenaf Bast Fibers. Fibers 2014, 2 (3) , 242-254. https://doi.org/10.3390/fib2030242
- I. Stachiv, J. Zapomel, Y.-L. Chen. Simultaneous determination of the elastic modulus and density/thickness of ultrathin films utilizing micro-/nanoresonators under applied axial force. Journal of Applied Physics 2014, 115 (12) , 124304. https://doi.org/10.1063/1.4869415
- Suchol Savagatrup, Aditya S. Makaram, Daniel J. Burke, Darren J. Lipomi. Mechanical Properties of Conjugated Polymers and Polymer-Fullerene Composites as a Function of Molecular Structure. Advanced Functional Materials 2014, 24 (8) , 1169-1181. https://doi.org/10.1002/adfm.201302646
- Manuel R. Mikczinski, Gabriella Josefsson, Gary Chinga-Carrasco, E. Kristofer Gamstedt, Sergej Fatikow. Nanorobotic Testing to Assess the Stiffness Properties of Nanopaper. IEEE Transactions on Robotics 2014, 30 (1) , 115-119. https://doi.org/10.1109/TRO.2013.2283409
- Andrew Marais, Simon Utsel, Emil Gustafsson, Lars Wågberg. Towards a super-strainable paper using the Layer-by-Layer technique. Carbohydrate Polymers 2014, 100 , 218-224. https://doi.org/10.1016/j.carbpol.2013.03.049
- Mrinal Bhattacharya, Sunayana Chaudhry. High-performance silica nanoparticle reinforced poly (vinyl alcohol) as templates for bioactive nanocomposites. Materials Science and Engineering: C 2013, 33 (5) , 2601-2610. https://doi.org/10.1016/j.msec.2013.02.029
- KEVIN H. M. KAN, EMILY D. CRANSTON. Mechanical testing of thin film nanocellulose composites using buckling mechanics. TAPPI Journal 2013, 12 (4) , 9-17. https://doi.org/10.32964/TJ12.4.9
- Erik Johansson, Lars Wågberg. Tailoring the mechanical properties of starch-containing layer-by-layer films. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2012, 394 , 14-22. https://doi.org/10.1016/j.colsurfa.2011.11.017
- Mohamed Eita, Hans Arwin, Hjalmar Granberg, Lars Wågberg. Addition of silica nanoparticles to tailor the mechanical properties of nanofibrillated cellulose thin films. Journal of Colloid and Interface Science 2011, 363 (2) , 566-572. https://doi.org/10.1016/j.jcis.2011.07.085



