Abstract
Cellulose nanofibrils (CNF) are a promising building block of structural materials because they are biodegradable, can be made into optically transparent bulk materials, and have exceptional specific strength and stiffness compared to common synthetic polymers. The manufacturing of bulk materials from CNFs is a challenge because CNFs form networks in solution at low solids concentration, which can result in long processing times as well as large residual stresses and distortion upon water removal. Here, a method to form materials from CNF suspensions via direct ink writing, a type of additive manufacturing, is demonstrated. Multilayer printing of CNFs provides a route to control drying time by depositing thin layers one at a time. A printing system with a pressure-controlled dispensing system was used to deposit aqueous CNF suspensions onto a temperature-controlled substrate. The geometry, roughness, and mechanical properties of the printed structures were characterized. The shape of the printed line profile is controlled by a combination of the wettability of the substrate, dispense rate, printing speed, and temperature of the substrate. Spatial variation of the elastic modulus of printed CNF structures was assessed with nanoindentation and the average percent difference was found to be small at ± 2.6% of the mean over the area of the printed lines. Through multilayer printing freestanding films with thicknesses greater than 60 μm were achieved. Tensile specimens were printed and characterized; a tensile strength of 72.6 MPa ± 7.4 MPa and a Young’s modulus of 10.2 GPa ± 1.2 GPa were measured.
Graphical abstract









Similar content being viewed by others
References
Aulin C, Salazar-Alvarez G, Lindström T (2012) High strength, flexible and transparent nanofibrillated cellulose–nanoclay biohybrid films with tunable oxygen and water vapor permeability. Nanoscale 4:6622. https://doi.org/10.1039/c2nr31726e
Baez C, Considine J, Rowlands R (2014) Influence of drying restraint on physical and mechanical properties of nanofibrillated cellulose films. Cellulose 21:347–356. https://doi.org/10.1007/s10570-013-0159-1
Barry RA, Shepherd RF, Hanson JN et al (2009) Direct-write assembly of 3D hydrogel scaffolds for guided cell growth. Adv Mater 21:2407–2410. https://doi.org/10.1002/adma.200803702
Berman B (2012) 3-D printing: the new industrial revolution. Bus Horiz 55:155–162. https://doi.org/10.1016/j.bushor.2011.11.003
Carpenter AW, de Lannoy C-F, Wiesner MR (2015) Cellulose nanomaterials in water treatment technologies. Environ Sci Technol 49:5277–5287. https://doi.org/10.1021/es506351r
Compton BG, Lewis JA (2014) 3D-printing of lightweight cellular composites. Adv Mater 26:5930–5935. https://doi.org/10.1002/adma.201401804
Fukuzumi H, Saito T, Iwata T et al (2009) Transparent and high gas barrier films of cellulose nanofibers prepared by TEMPO-mediated oxidation transparent and high gas barrier films of cellulose nanofibers prepared by TEMPO-mediated oxidation. Biomacromol 10:162–165. https://doi.org/10.1021/bm801065u
Gladman AS, Matsumoto EA, Nuzzo RG et al (2016) Biomimetic 4D printing. Nat Mater 15:413–418. https://doi.org/10.1038/nmat4544
Gross BC, Erkal JL, Lockwood SY et al (2014) Evaluation of 3D printing and its potential impact on biotechnology and the chemical sciences. Anal Chem 86:3240–3253. https://doi.org/10.1021/ac403397r
Hakansson KMO, Henriksson IC, de la Peña Vazquez C et al (2016) Solidification of 3D printed nanofibril hydrogels into functional 3D cellulose structures. Adv Mater Technol. https://doi.org/10.1080/01425690701737481
Hardin JO, Ober TJ, Valentine AD, Lewis JA (2015) Microfluidic printheads for multimaterial 3D printing of viscoelastic inks. Adv Mater 27:3279–3284. https://doi.org/10.1002/adma.201500222
Henriksson M, Berglund LA, Isaksson P et al (2008) Cellulose nanopaper structures of high toughness. Biomacromol 9:1579–1585. https://doi.org/10.1021/bm800038n
Isogai A (2013) Wood nanocelluloses: fundamentals and applications as new bio-based nanomaterials. J Wood Sci 59:449–459. https://doi.org/10.1007/s10086-013-1365-z
Isogai A, Bergstrom L (2018) Preparation of cellulose nanofibers using green and sustainable chemistry. Curr Opin Green Sustain Chem 12:15–21
Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85. https://doi.org/10.1039/c0nr00583e
Kacir L, Narkis M, Ishai O (1975) Oriented short glass-fiber composites. II. Analysis of parameters controlling the fiber/glycerine orientation process. Polym Eng Sci 15:532–537. https://doi.org/10.1002/pen.760150709
Lewis JA, Gratson GM (2004) Direct writing in three dimensions. Mater Today 7:32–39. https://doi.org/10.1016/S1369-7021(04)00344-X
Malho JM, Laaksonen P, Walther A et al (2012) Facile method for stiff, tough, and strong nanocomposites by direct exfoliation of multilayered graphene into native nanocellulose matrix. Biomacromol 13:1093–1099. https://doi.org/10.1021/bm2018189
Marksteadt K, Sundberg J, Gatenholm P (2014) 3D bioprinting of cellulose structures from an ionic liquid. 3D Print Addit Manuf. https://doi.org/10.1080/01425690701737481
Mashkour M, Kimura T, Kimura F et al (2014) Tunable self-assembly of cellulose nanowhiskers and polyvinyl alcohol chains induced by surface tension torque. Biomacromol 15:60–65. https://doi.org/10.1021/bm401287s
Okuzono T, Kobayashi M, Doi M (2009) Final shape of a drying thin film. Phys Rev E Stat Nonlinear Soft Matter Phys 80:1–11. https://doi.org/10.1103/PhysRevE.80.021603
Oliver WC, Pharr GM (1992) An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. J Mater Res 7:1564–1583. https://doi.org/10.1557/JMR.1992.1564
Pääkkö M, Ankerfors M, Kosonen H et al (2007) Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels. Biomacromol 8:1934–1941. https://doi.org/10.1021/bm061215p
Pattinson SW, Hart AJ (2017) Additive manufacturing of cellulosic materials with robust mechanics and antimicrobial functionality. Adv Mater Technol 2:1600084. https://doi.org/10.1002/admt.201600084
Pauchard L, Allain C (2003) Buckling instability induced by polymer solution drying. Euorphysics Lett 62:897–903. https://doi.org/10.1209/epl/i2005-10093-3
Qing Y, Sabo R, Zhu JY et al (2013) A comparative study of cellulose nanofibrils disintegrated via multiple processing approaches. Carbohydr Polym 97:226–234. https://doi.org/10.1016/j.carbpol.2013.04.086
Rees A, Powell LC, Chinga-Carrasco G et al (2015) 3D bioprinting of carboxymethylated-periodate oxidized nanocellulose constructs for wound dressing applications. Biomed Res Int. https://doi.org/10.1155/2015/925757
Reiner RS, Rudie AW (2013) Pilot plant scale-up of TEMPO pretreated cellulose nanofibrils. In: Postek M, Moon RJ, Rudie AW, Bilodeau MA (eds) Production and applications of cellulose nanomaterials. TAPPI Press, Peachtree Corners, pp 177–178
Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromol 8:2485–2491. https://doi.org/10.1021/bm0703970
Sehaqui H, Ezekiel Mushi N, Morimune S et al (2012) Cellulose nanofiber orientation in nanopaper and nanocomposites by cold drawing. ACS Appl Mater Interfaces 4:1043–1049. https://doi.org/10.1021/am2016766
Shatkin JA, Wegner TH, Bilek EM, Cowie J (2014) Market projections of cellulose nanomaterial-enabled products—Part 1: applications. Nanocellulose Mark 13:9–16
Siqueira G, Kokkinis D, Libanori R et al (2017) Cellulose nanocrystal inks for 3D printing of textured cellular architectures. Adv Funct Mater 27:1604619. https://doi.org/10.1002/adfm.201604619
Skogberg A, Mäki AJ, Mettänen M et al (2017) Cellulose nanofiber alignment using evaporation-induced droplet-casting, and cell alignment on aligned nanocellulose surfaces. Biomacromol 18:3936–3953. https://doi.org/10.1021/acs.biomac.7b00963
Suhling JC (1985) Constitutive relations and failure predictions for nonlinear orthotropic media, vol 1. University of Wisconsin-Madison, Madison
Wang Q, Sun J, Yao Q et al (2018) 3D printing with cellulose materials. Cellulose. https://doi.org/10.1007/s10570-018-1888-y
Wu CN, Saito T, Fujisawa S et al (2012) Ultrastrong and high gas-barrier nanocellulose/clay-layered composites. Biomacromol 13:1927–1932. https://doi.org/10.1021/bm300465d
Zhu H, Zhu S, Jia Z et al (2015) Anomalous scaling law of strength and toughness of cellulose nanopaper. Proc Natl Acad Sci 112:8971–8976. https://doi.org/10.1073/pnas.1502870112
Acknowledgments
This work was supported by the U.S. Endowment for Forestry and Communities, Inc. as part of the P3Nano program. This work was performed in part at the University of Pennsylvania’s Singh Center for Nanotechnology, an NNCI member supported by NSF Grant ECCS-1542153. The authors thank Dr. Joseph E. Jakes (USDA Forest Service, Forest Products Laboratory) for insightful nanoindentation discussions. The authors also thank Dr. Alexander I. Bennett (University of Pennsylvania) for helpful discussions and assistance in preparing Figs. 1 and 2.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Mariani, L.M., Johnson, W.R., Considine, J.M. et al. Printing and mechanical characterization of cellulose nanofibril materials. Cellulose 26, 2639–2651 (2019). https://doi.org/10.1007/s10570-019-02247-w
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-019-02247-w
