Abstract
Cellulose nanofibrils (CNFs) have been widely used as a nanofiller for polymer composite reinforcement due to their excellent mechanical properties. However, CNF is produced in water and needs to be dried prior to use in composite materials. The presence of hydroxyl groups on the surface of CNF creates strong hydrogen bonding that makes it difficult and costly to dry. Additionally, the hydrophilicity at the fiber surface results in agglomeration of CNFs within many polymer matrices. In this study, chitosan (CS) was co-precipitated with CNF to produce a dual-bonding filler for use in poly (lactic acid) (PLA) composites. CS promotes improved interfacial interaction within the polymer matrix by forming strong hydrogen bonds with the CNF and potential covalent bonds with the PLA. The results confirmed that the addition of a small amount of CS significantly improved the mechanical properties compared to PLA + CNF composites and neat PLA. The detailed study of the PLA + CNF/CS composites reveals the synergetic effect of the hydrogen and covalent bonding mechanism for PLA reinforcement.
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References
Abdul Khalil HPS, Bhat AH, Ireana Yusra AF (2012) Green composites from sustainable cellulose nanofibrils: a review. Carbohydr Polym 87:963–979. https://doi.org/10.1016/j.carbpol.2011.08.078
Abitbol T, Rivkin A, Cao Y, Nevo Y, Abraham E, Ben-Shalom T, Lapidot S, Shoseyov O (2016) Nanocellulose, a tiny fiber with huge applications. Curr Opin Biotechnol 39:76–88. https://doi.org/10.1016/j.copbio.2016.01.002
Abdul Khalil HPS, Saurabh CK, Adnan AS, Nurul Fazita MR, Syakir MI, Davoudpour Y, Rafatullah M, Abdullah CK, Haafiz MKM, Dungani R (2016) A review on chitosan-cellulose blends and nanocellulose reinforced chitosan biocomposites: Properties and their applications. Carbohydr Polym 150:216–226. https://doi.org/10.1016/j.carbpol.2016.05.028
Ali Raza Z, Anwar F, Hussain I, Abid S, Masood R, Shahzad Maqsood H (2019) Fabrication of PLA incorporated chitosan nanoparticles to create enhanced functional properties of cotton fabric. Pigm Resin Technol 48:169–177. https://doi.org/10.1108/PRT-11-2017-0088
An N, Wang X, Li Y, Zhang L, Lu Z, Sun J (2019) Healable and mechanically super-strong polymeric composites derived from hydrogen-bonded polymeric complexes. Adv Mater 31:1904882. https://doi.org/10.1002/adma.201904882
Bakshi PS, Selvakumar D, Kadirvelu K, Kumar NS (2020) Chitosan as an environment friendly biomaterial – a review on recent modifications and applications. Int J Biol Macromol 150:1072–1083. https://doi.org/10.1016/j.ijbiomac.2019.10.113
Beaumont M, König J, Opietnik M, Potthast A, Rosenau T (2017) Drying of a cellulose II gel: effect of physical modification and redispersibility in water. Cellulose 24:1199–1209. https://doi.org/10.1007/s10570-016-1166-9
Bréchet Y, Cavaillé JY, Chabert E, Chazeau L, Dendievel R, Flandin L, Gauthier C (2001) Polymer based nanocomposites: effect of filler-filler and filler-matrix interactions. Adv Eng Mater 3:571–577. https://doi.org/10.1002/1527-2648(200108)3:8%3c571::Aid-adem571%3e3.0.Co;2-m
Cai W, Xue W, Jiang Y (2018) Facile preparation of magnetic chitosan coprecipitated by ethanol/NH3·H2O for highly efficient removal toward Cr(VI). ACS Omega 3:5725–5734. https://doi.org/10.1021/acsomega.8b00393
Conder JR, Young CL (1979) Physicochemical measurement by gas chromatography. John Wiley & Sons
Fowkes FM (1964) Attractive forces at interfaces. Ind Eng Chem 56:40–52. https://doi.org/10.1021/ie50660a008
Fujisawa S, Saito T, Kimura S, Iwata T, Isogai A (2013) Surface engineering of ultrafine cellulose nanofibrils toward polymer nanocomposite materials. Biomacromol 14:1541–1546. https://doi.org/10.1021/bm400178m
Gutmann V (1978) Donor-acceptor approach to molecular interactions. Plenum press
Habibi Y (2014) Key advances in the chemical modification of nanocelluloses. Chem Soc Rev 43:1519–1542. https://doi.org/10.1039/c3cs60204d
Hu X, Vatankhah-Varnoosfaderani M, Zhou J, Li Q, Sheiko SS (2015) Weak hydrogen bonding enables hard, strong, tough, and elastic hydrogels. Adv Mater 27:6899–6905. https://doi.org/10.1002/adma.201503724
Isogai A (2020) Emerging nanocellulose technologies: recent developments. Adv Mater. https://doi.org/10.1002/adma.202000630
Jawaid M, Boufi S, Abdul Khalil HPS (Eds) (2017) Cellulose-reinforced nanofibre composites: production, properties and applications. Woodhead Publishing series in composites science and engineering. Elsevier, Woodhead Publishing, United Kingdom
Kalia S, Boufi S, Celli A, Kango S (2013) Nanofibrillated cellulose: surface modification and potential applications. Coll Polym Sci 292:5–31. https://doi.org/10.1007/s00396-013-3112-9
Kamaludin NHI, Ismail H, Rusli A, Ting SS (2021) Thermal behavior and water absorption kinetics of polylactic acid/chitosan biocomposites. Iran Polym J 30:135–147. https://doi.org/10.1007/s13726-020-00879-5
Lamm ME, Song L, Wang Z, Rahman MA, Lamm B, Fu L, Tang C (2019) Tuning mechanical properties of biobased polymers by supramolecular chain entanglement. Macromolecules 52:8967–8975. https://doi.org/10.1021/acs.macromol.9b01828
Lamm ME, Li K, Qian J, Wang L, Lavoine N, Newman R, Gardner DJ, Li T, Hu L, Ragauskas AJ, Tekinalp H, Kunc V, Ozcan S (2021) Recent advances in functional materials through cellulose nanofiber templating. Adv Mater 33:e2005538. https://doi.org/10.1002/adma.202005538
Li K, Skolrood L, Aytug T, Tekinalp H, Ozcan S (2019) Strong and tough cellulose nanofibrils composite films: mechanism of synergetic effect of hydrogen bonds and ionic interactions. ACS Sustain Chem Eng 7:14341–14346. https://doi.org/10.1021/acssuschemeng.9b03442
Li K, Clarkson CM, Wang L, Liu Y, Lamm M, Pang Z, Zhou Y, Qian J, Tajvidi M, Gardner DJ, Tekinalp H, Hu L, Li T, Ragauskas AJ, Youngblood JP, Ozcan S (2021a) Alignment of cellulose nanofibers: harnessing nanoscale properties to macroscale benefits. ACS Nano 15:3646–3673. https://doi.org/10.1021/acsnano.0c07613
Li K, McGrady D, Zhao X, Ker D, Tekinalp H, He X, Qu J, Aytug T, Cakmak E, Phipps J, Ireland S, Kunc V, Ozcan S (2021b) Surface-modified and oven-dried microfibrillated cellulose reinforced biocomposites: cellulose network enabled high performance. Carbohydr Polym 256:117525. https://doi.org/10.1016/j.carbpol.2020.117525
Liu D, Sun X, Tian H, Maiti S, Ma Z (2013) Effects of cellulose nanofibrils on the structure and properties on PVA nanocomposites. Cellulose 20:2981–2989. https://doi.org/10.1007/s10570-013-0073-6
Lu Y, Cueva MC, Lara-Curzio E, Ozcan S (2015) Improved mechanical properties of polylactide nanocomposites-reinforced with cellulose nanofibrils through interfacial engineering via amine-functionalization. Carbohydr Polym 131:208–217. https://doi.org/10.1016/j.carbpol.2015.05.047
Meng XT, Bocharova V, Tekinalp H, Cheng SW, Kisliuk A, Sokolov AP, Kunc V, Peter WH, Ozcan S (2018) Toughening of nanocelluose/PLA composites via bio-epoxy interaction: mechanistic study. Mater Design 139:188–197. https://doi.org/10.1016/j.matdes.2017.11.012
Missoum K, Belgacem MN, Bras J (2013) Nanofibrillated cellulose surface modification: a review. Materials (basel) 6:1745–1766. https://doi.org/10.3390/ma6051745
Nechyporchuk O, Belgacem MN, Bras J (2016) Production of cellulose nanofibrils: a review of recent advances. Ind Crops Prod 93:2–25. https://doi.org/10.1016/j.indcrop.2016.02.016
Niu X, Liu Y, Song Y, Han J, Pan H (2018) Rosin modified cellulose nanofiber as a reinforcing and co-antimicrobial agents in polylactic acid /chitosan composite film for food packaging. Carbohydr Polym 183:102–109. https://doi.org/10.1016/j.carbpol.2017.11.079
Pan P, Kai W, Zhu B, Dong T, Inoue Y (2007) Polymorphous crystallization and multiple melting behavior of poly(l-lactide): molecular weight dependence. Macromolecules 40:6898–6905. https://doi.org/10.1021/ma071258d
Pan P, Zhu B, Kai W, Dong T, Inoue Y (2008) Polymorphic transition in disordered poly(l-lactide) crystals induced by annealing at elevated temperatures. Macromolecules 41:4296–4304. https://doi.org/10.1021/ma800343g
Peng YC, Gardner DJ, Han YS (2012) Drying cellulose nanofibrils: in search of a suitable method. Cellulose 19:91–102. https://doi.org/10.1007/s10570-011-9630-z
Peng Y, Gardner DJ, Han Y, Cai Z, Tshabalala MA (2013) Influence of drying method on the surface energy of cellulose nanofibrils determined by inverse gas chromatography. J Coll Interface Sci 405:85–95. https://doi.org/10.1016/j.jcis.2013.05.033
Peng J, Ellingham T, Sabo R, Turng L-S, Clemons CM (2014) Short cellulose nanofibrils as reinforcement in polyvinyl alcohol fiber. Cellulose 21:4287–4298. https://doi.org/10.1007/s10570-014-0411-3
Peresin MS, Habibi Y, Zoppe JO, Pawlak JJ, Rojas OJ (2010) Nanofiber composites of polyvinyl alcohol and cellulose nanocrystals: manufacture and characterization. Biomacromol 11:674–681. https://doi.org/10.1021/bm901254n
Pu S, Hou Y, Yan C, Ma H, Huang H, Shi Q, Mandal S, Diao Z, Chu W (2018) In situ coprecipitation formed highly water-dispersible magnetic chitosan nanopowder for removal of heavy metals and its adsorption mechanism. ACS Sustain Chem Eng 6:16754–16765. https://doi.org/10.1021/acssuschemeng.8b04028
Rinaudo M (2006) Chitin and chitosan: properties and applications. Prog Polym Sci 31:603–632. https://doi.org/10.1016/j.progpolymsci.2006.06.001
Rizal S, Saharudin NI, Olaiya NG, Khalil HPSA, Haafiz MKM, Ikramullah I, Muksin U, Olaiya FG, Abdullah CK, Yahya EB (2021) Functional properties and molecular degradation of schizostachyum brachycladum bamboo cellulose nanofibre in PLA-chitosan bionanocomposites. Molecules 26:2008
Rol F, Belgacem MN, Gandini A, Bras J (2019) Recent advances in surface-modified cellulose nanofibrils. Prog Polym Sci 88:241–264. https://doi.org/10.1016/j.progpolymsci.2018.09.002
Schultz J, Lavielle L, Martin C (1987) The role of the interface in carbon fibre-epoxy composites. J Adhes 23:45–60. https://doi.org/10.1080/00218468708080469
Shah BL, Selke SE, Walters MB, Heiden PA (2008) Effects of wood flour and chitosan on mechanical, chemical, and thermal properties of polylactide. Polym Compos 29:655–663. https://doi.org/10.1002/pc.20415
Sinquefield S, Ciesielski PN, Li K, Gardner DJ, Ozcan S (2020) Nanocellulose dewatering and drying: current state and future perspectives. ACS Sustain Chem Eng 8:9601–9615. https://doi.org/10.1021/acssuschemeng.0c01797
Tekinalp HL, Meng X, Lu Y, Kunc V, Love LJ, Peter WH, Ozcan S (2019) High modulus biocomposites via additive manufacturing: Cellulose nanofibril networks as “microsponges.” Compos B Eng. https://doi.org/10.1016/j.compositesb.2019.05.028
Wang L, Gardner DJ, Bousfield DW (2018a) Cellulose nanofibril-reinforced polypropylene composites for material extrusion: rheological properties. Polym Eng Sci 58:793–801. https://doi.org/10.1002/pen.24615
Wang L, Roach AW, Gardner DJ, Han Y (2018b) Mechanisms contributing to mechanical property changes in composites of polypropylene reinforced with spray-dried cellulose nanofibrils. Cellulose 25:439–448. https://doi.org/10.1007/s10570-017-1556-7
Wang L, Gardner DJ, Wang J, Yang Y, Tekinalp HL, Tajvidi M, Li K, Zhao X, Neivandt DJ, Han Y, Ozcan S, Anderson J (2020) Towards industrial-scale production of cellulose nanocomposites using melt processing: a critical review on structure-processing-property relationships. Compos B Eng 201:108297. https://doi.org/10.1016/j.compositesb.2020.108297
Zhao X, Li K, Wang Y, Tekinalp H, Richard A, Webb E, Ozcan S (2020) Bio-treatment of poplar via amino acid for interface control in biocomposites. Compos B Eng 199:108276. https://doi.org/10.1016/j.compositesb.2020.108276
Zhou Y, Fan M, Chen L (2016) Interface and bonding mechanisms of plant fibre composites: an overview. Compos B Eng 101:31–45. https://doi.org/10.1016/j.compositesb.2016.06.055
Zimmermann MVG, Borsoi C, Lavoratti A, Zanini M, Zattera AJ, Santana RMC (2016) Drying techniques applied to cellulose nanofibers. J Reinf Plast Compos 35:628–643. https://doi.org/10.1177/0731684415626286
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This research was supported by the U.S. Department of Energy (DOE), Advanced Manufacturing Office and used resources at the Manufacturing Demonstration Facility at Oak Ridge National Laboratory, a User Facility of DOE’s Office of Energy Efficiency and Renewable Energy. This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). Microscopy studies were completed at the Center for Nanophase Materials Sciences, a DOE Office of Science User Facility. Authors thank Dr. Harry Meyer for his help on XPS measurement and Dr. Yunqiao Pu for his help on solid state NMR measurement.
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This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy.
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MEL: Methodology, Writing—original draft, Writing—review & editing. KL: Conceptualization, Methodology, Software, Writing—review & editing. DK: Investigation. XZ: Investigation, Writing—review & editing. HEH: Investigation. KC: Formal analysis, Writing—review & editing. HT: Writing—review & editing. SO: Writing—review & editing, Supervision, Funding acquisition.
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Lamm, M.E., Li, K., Ker, D. et al. Exploiting chitosan to improve the interface of nanocellulose reinforced polymer composites. Cellulose 29, 3859–3870 (2022). https://doi.org/10.1007/s10570-021-04327-2
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DOI: https://doi.org/10.1007/s10570-021-04327-2