Abstract
Cellulose nanopaper exhibits outstanding stiffness, strength, and toughness that originate from the exceptional properties of constituent cellulose nanocrystals (CNCs). However, it remains challenging to link the nanoscale properties of rod-like CNCs and their structural arrangements to the macroscale performance of nanopaper in a predictive manner. Here we address this need by establishing an atomistically informed coarse-grained model for CNCs via a strain energy conservation paradigm and simulating CNC nanopaper properties mesoscopically. We predict how the mechanical properties of CNC nanopaper with nacre-inspired brick-and-mortar structure depend on CNC overlap length and interfacial energy. We show that the modulus and strength both increase with increasing overlap length, but saturate at different critical length scales where a transition from non-covalent interfacial sliding to CNCs fracture is the key influencing mechanism. Maximum toughness is achieved when the interface and CNC failure are tuned to occur at the same time through balanced failure. We propose strategies for maximizing nanopaper mechanical performance by tuning interfacial interactions of constitutive CNCs through surface modifications that improve shear transfer capability. Our model generates broadly applicable insights into factors governing the performance of self-assembling paper materials made from 1D nanostructures.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Explore related subjects
Discover the latest articles and news from researchers in related subjects, suggested using machine learning.References
Bras J, Viet D, Bruzzese C, Dufresne A (2011) Correlation between stiffness of sheets prepared from cellulose whiskers and nanoparticles dimensions. Carbohydr Polym 84:211–215. doi:10.1016/j.carbpol.2010.11.022
Brooks BR et al (2009) CHARMM: the biomolecular simulation program. J Comput Chem 30:1545–1614. doi:10.1002/jcc.21287
Buehler MJ (2006) Mesoscale modeling of mechanics of carbon nanotubes: self-assembly, self-folding, and fracture. J Mater Res 21:2855–2869
Cao C, Daly M, Chen B, Howe JY, Singh CV, Filleter T, Sun Y (2015) Strengthening in graphene oxide nanosheets: bridging the gap between interplanar and intraplanar fracture. Nano Lett 15:6528–6534. doi:10.1021/acs.nanolett.5b02173
Capadona JR, Shanmuganathan K, Tyler DJ, Rowan SJ, Weder C (2008) Stimuli-responsive polymer nanocomposites inspired by the sea cucumber dermis. Science 319:1370–1374. doi:10.1126/science.1153307
Cranford SW, Buehler MJ (2010) In silico assembly and nanomechanical characterization of carbon nanotube buckypaper. Nanotechnology 21:265706. doi:10.1088/0957-4484/21/26/265706
D’Elia E, Eslava S, Miranda M, Georgiou TK, Saiz E (2016) Autonomous self-healing structural composites with bio-inspired design. Sci Rep 6:25059. doi:10.1038/srep25059
Diddens I, Murphy B, Krisch M, Müller M (2008) Anisotropic elastic properties of cellulose measured using inelastic x-ray scattering. Macromolecules 41:9755–9759. doi:10.1021/ma801796u
Dong H et al (2015) Highly transparent and toughened poly(methyl methacrylate) nanocomposite films containing networks of cellulose nanofibrils. ACS Appl Mater Interfaces 7:25464–25472. doi:10.1021/acsami.5b08317
Dumanli AG, van der Kooij HM, Kamita G, Reisner E, Baumberg JJ, Steiner U, Vignolini S (2014) Digital color in cellulose nanocrystal films. ACS Appl Mater Interfaces 6:12302–12306. doi:10.1021/am501995e
Eichhorn SJ (2011) Cellulose nanowhiskers: promising materials for advanced applications. Soft Matter 7:303–315. doi:10.1039/C0SM00142B
Elazzouzi-Hafraoui S, Nishiyama Y, Putaux J-L, Heux L, Dubreuil F, Rochas C (2008) The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose. Biomacromolecules 9:57–65. doi:10.1021/bm700769p
Fox DM et al (2016) Simultaneously tailoring surface energies and thermal stabilities of cellulose nanocrystals using ion exchange: effects on polymer composite properties for transportation infrastructure, and renewable energy applications. ACS Appl Mater Interfaces 8:27270–27281. doi:10.1021/acsami.6b06083
Fratzl P (2007) Biomimetic materials research: what can we really learn from nature’s structural materials? J R Soc Interface 4:637–642. doi:10.1098/rsif.2007.0218
Gao H, Ji B, Jäger IL, Arzt E, Fratzl P (2003) Materials become insensitive to flaws at nanoscale: lessons from nature. Proc Natl Acad Sci 100:5597–5600. doi:10.1073/pnas.0631609100
Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110:3479–3500
Henriksson M, Berglund LA, Isaksson P, Lindström T, Nishino T (2008) Cellulose nanopaper structures of high toughness. Biomacromolecules 9:1579–1585. doi:10.1021/bm800038n
Hsu DD, Xia W, Arturo SG, Keten S (2014) Systematic method for thermomechanically consistent coarse-graining: a universal model for methacrylate-based polymers. J Chem Theory Comput 10:2514–2527. doi:10.1021/ct500080h
Huang P, Zhao Y, Kuga S, Wu M, Huang Y (2016) A versatile method for producing functionalized cellulose nanofibers and their application. Nanoscale 8:3753–3759. doi:10.1039/C5NR08179C
Humphrey W, Dalke A, Schulten K (1996) VMD: visual molecular dynamics. J Mol Graph 14:33–38. doi:10.1016/0263-7855(96)00018-5
Isogai A (2013) Wood nanocelluloses: fundamentals and applications as new bio-based nanomaterials. J Wood Sci 59:449–459. doi:10.1007/s10086-013-1365-z
Kelly JA, Giese M, Shopsowitz KE, Hamad WY, MacLachlan MJ (2014) The development of chiral nematic mesoporous materials. Acc Chem Res 47:1088–1096. doi:10.1021/ar400243m
Kulasinski K, Guyer R, Keten S, Derome D, Carmeliet J (2015) Impact of moisture adsorption on structure and physical properties of amorphous biopolymers. Macromolecules. doi:10.1021/acs.macromol.5b00248
Lagerwall JPF, Schutz C, Salajkova M, Noh J, Hyun Park J, Scalia G, Bergstrom L (2014) Cellulose nanocrystal-based materials: from liquid crystal self-assembly and glass formation to multifunctional thin films. NPG Asia Mater 6:e80. doi:10.1038/am.2013.69
Li Y, Kröger M (2012) A theoretical evaluation of the effects of carbon nanotube entanglement and bundling on the structural and mechanical properties of buckypaper. Carbon 50:1793–1806. doi:10.1016/j.carbon.2011.12.027
Liu Y, Xie B, Zhang Z, Zheng Q, Xu Z (2012) Mechanical properties of graphene papers. J Mech Phys Solids 60:591–605. doi:10.1016/j.jmps.2012.01.002
Liu Y, Li Y, Yang G, Zheng X, Zhou S (2015) Multi-stimulus-responsive shape-memory polymer nanocomposite network cross-linked by cellulose nanocrystals. ACS Appl Mater Interfaces 7:4118–4126. doi:10.1021/am5081056
Majoinen J, Kontturi E, Ikkala O, Gray DG (2012) SEM imaging of chiral nematic films cast from cellulose nanocrystal suspensions. Cellulose 19:1599–1605
Meng Z, Soler-Crespo RA, Xia W, Gao W, Ruiz L, Espinosa HD, Keten S (2017) A coarse-grained model for the mechanical behavior of graphene oxide. Carbon 117:476–487. doi:10.1016/j.carbon.2017.02.061
Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994. doi:10.1039/c0cs00108b
Mtibe A, Linganiso LZ, Mathew AP, Oksman K, John MJ, Anandjiwala RD (2015) A comparative study on properties of micro and nanopapers produced from cellulose and cellulose nanofibres. Carbohydr Polym 118:1–8. doi:10.1016/j.carbpol.2014.10.007
Nikolov S et al (2010) Revealing the design principles of high-performance biological composites using Ab initio and multiscale simulations: the example of lobster cuticle. Adv Mater 22:519–526. doi:10.1002/adma.200902019
Noid WG (2013) Perspective: coarse-grained models for biomolecular systems. J Chem Phys 139:090901. doi:10.1063/1.4818908
Pan J, Hamad W, Straus SK (2010) Parameters affecting the chiral nematic phase of nanocrystalline cellulose films. Macromolecules 43:3851–3858. doi:10.1021/ma902383k
Phillips JC et al (2005) Scalable molecular dynamics with NAMD. J Comput Chem 26:1781–1802. doi:10.1002/jcc.20289
Plimpton S (1995) Fast parallel algorithms for short-range molecular dynamics. J Comput Phys 117:1–19. doi:10.1006/jcph.1995.1039
Qin X, Xia W, Sinko R, Keten S (2015) Tuning glass transition in polymer nanocomposites with functionalized cellulose nanocrystals through nanoconfinement. Nano Lett 15:6738–6744. doi:10.1021/acs.nanolett.5b02588
Ramanathan T et al (2008) Functionalized graphene sheets for polymer nanocomposites. Nat Nanotechnol 3:327–331. doi:10.1038/nnano.2008.96
Reising AB, Moon RJ, Youngblood JP (2012) Effect of particle alignment on mechanical properties of neat cellulose nanocrystal films. J Sci Technol Forest Prod Process 2:32–41
Ruiz L, Xia W, Meng Z, Keten S (2015) A coarse-grained model for the mechanical behavior of multi-layer graphene. Carbon 82:103–115. doi:10.1016/j.carbon.2014.10.040
Saito T, Uematsu T, Kimura S, Enomae T, Isogai A (2011) Self-aligned integration of native cellulose nanofibrils towards producing diverse bulk materials. Soft Matter 7:8804–8809. doi:10.1039/C1SM06050C
Sehaqui H, Liu A, Zhou Q, Berglund LA (2010) Fast preparation procedure for large flat cellulose and cellulose/inorganic nanopaper structures. Biomacromolecules 11:2195–2198. doi:10.1021/bm100490s
Sehaqui H, Zhou Q, Ikkala O, Berglund LA (2011) Strong and tough cellulose nanopaper with high specific surface area and porosity. Biomacromolecules 12:3638–3644. doi:10.1021/bm2008907
Sehaqui H, Ezekiel Mushi N, Morimune S, Salajkova M, Nishino T, Berglund LA (2012) Cellulose nanofiber orientation in nanopaper and nanocomposites by cold drawing. ACS Appl Mater Interfaces 4:1043–1049. doi:10.1021/am2016766
Shao C, Keten S (2015) Stiffness enhancement in nacre-inspired nanocomposites due to nanoconfinement. Sci Rep 5:16452. doi:10.1038/srep16452
Shopsowitz KE, Stahl A, Hamad WY, MacLachlan MJ (2012) Hard templating of nanocrystalline titanium dioxide with chiral nematic ordering. Angew Chem Int Ed 51:6886–6890. doi:10.1002/anie.201201113
Sinko R, Keten S (2014) Effect of moisture on the traction-separation behavior of cellulose nanocrystal interfaces. Appl Phys Lett 105:243702. doi:10.1063/1.4904708
Sinko R, Keten S (2015) Traction–separation laws and stick–slip shear phenomenon of interfaces between cellulose nanocrystals. J Mech Phys Solids 78:526–539. doi:10.1016/j.jmps.2015.02.012
Sinko R, Mishra S, Ruiz L, Brandis N, Keten S (2013) Dimensions of biological cellulose nanocrystals maximize fracture strength. ACS Macro Lett 3:64–69. doi:10.1021/mz400471y
Sinko R, Qin X, Keten S (2015) Interfacial mechanics of cellulose nanocrystals. MRS Bull 40:340–348. doi:10.1557/mrs.2015.67
Song ZQ, Ni Y, Peng LM, Liang HY, He LH (2016) Interface failure modes explain non-monotonic size-dependent mechanical properties in bioinspired nanolaminates. Sci Rep 6:23724. doi:10.1038/srep23724
Šturcová A, Davies GR, Eichhorn SJ (2005) Elastic modulus and stress-transfer properties of tunicate cellulose whiskers. Biomacromolecules 6:1055–1061. doi:10.1021/bm049291k
Trache D, Hussin MH, Haafiz MKM, Thakur VK (2017) Recent progress in cellulose nanocrystals: sources and production. Nanoscale 9:1763–1786. doi:10.1039/C6NR09494E
Wang B, Torres-Rendon JG, Yu J, Zhang Y, Walther A (2015) Aligned bioinspired cellulose nanocrystal-based nanocomposites with synergetic mechanical properties and improved hygromechanical performance. ACS Appl Mater Interfaces 7:4595–4607. doi:10.1021/am507726t
Weaver JC et al (2012) The stomatopod dactyl club: a formidable damage-tolerant biological hammer. Science 336:1275–1280. doi:10.1126/science.1218764
Wegst UGK, Bai H, Saiz E, Tomsia AP, Ritchie RO (2015) Bioinspired structural materials. Nat Mater 14:23–36. doi:10.1038/nmat4089
Wei X, Naraghi M, Espinosa HD (2012) Optimal length scales emerging from shear load transfer in natural materials: application to carbon-based nanocomposite design. ACS Nano 6:2333–2344. doi:10.1021/nn204506d
Wu X, Moon R, Martini A (2014) Tensile strength of Iβ crystalline cellulose predicted by molecular dynamics simulation. Cellulose 21:2233–2245. doi:10.1007/s10570-014-0325-0
Xia W, Mishra S, Keten S (2013) Substrate vs. free surface: competing effects on the glass transition of polymer thin films. Polymer 54:5942–5951. doi:10.1016/j.polymer.2013.08.013
Xia W, Ruiz L, Pugno NM, Keten S (2016) Critical length scales and strain localization govern the mechanical performance of multi-layer graphene assemblies. Nanoscale 8:6456–6462. doi:10.1039/C5NR08488A
Xie B, Liu Y, Ding Y, Zheng Q, Xu Z (2011) Mechanics of carbon nanotube networks: microstructural evolution and optimal design. Soft Matter 7:10039. doi:10.1039/c1sm06034a
Zhu H et al. (2015) Anomalous scaling law of strength and toughness of cellulose nanopaper. Proc Natl Acad Sci:201502870 doi:10.1073/pnas.1502870112
Acknowledgments
The authors acknowledge funding from the Army Research Office (award# W911NF-13-1-0241), and the Center for Hierarchical Materials Design (CHiMAD) funded by National Institute of Standards and Technology (award# 70NANB14H012). Authors acknowledge support from the Dept. of Civil and Environmental Engineering and Dept. of Mechanical Engineering at Northwestern University, as well as a supercomputing grant from Northwestern University High Performance Computing Center.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Qin, X., Feng, S., Meng, Z. et al. Optimizing the mechanical properties of cellulose nanopaper through surface energy and critical length scale considerations. Cellulose 24, 3289–3299 (2017). https://doi.org/10.1007/s10570-017-1367-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-017-1367-x