Abstract
Cellulose-acetate nanofibers (CA-NF) and regenerated cellulose nanofibers (RC-NF) were separately compounded as reinforcement materials for enhancement of the mechanical property of polylactide (PLA). PLA has a great potential as an alternative to widely-used plastics such as polystyrene and poly(ethylene terephthalate), which are made from petroleum. PLA is well known for its biodegradability and renewability, but the mechanical property of PLA is not sufficient for industrial applications. In this study, CA-NF were successfully fabricated by electrospinning using 20 wt% cellulose-acetate solution with acetone/N,N-dimethylacetamide (6/4, wt/wt) mixture solvent, and RC-NF were synthesized by subsequent saponification, as reinforcement materials for PLA composites. The Young’s modulus of CA-NF/PLA composites increased linearly from 1670 to 1840 MPa with the increase in the nanofiber concentration to 15 wt%. In contrast, the Young’s modulus of RC-NF/PLA composites rapidly increased to ~ 1840 MPa at the relatively low nanofiber concentration of 5.0 wt%. Above 5.0 wt%, the Young’s modulus became stable and almost constant. RC-NF exhibited better reinforcing efficiency due to the excellent mechanical property of RC-NF, although the interfacial compatibility of RC-NF for PLA matrix was relatively poor as compared with that of CA-NF.
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References
Allen FH, Baalham CA, Lommerse JPM, Raithby PR (1998) Carbonyl–carbonyl interactions can be competitive with hydrogen bonds. Acta Crystallogr Sect B 54:320–329. https://doi.org/10.1107/S0108768198001463
Buffet J-C, Kapelski A, Okuda J (2010) Stereoselective polymerization of meso-lactide: syndiotactic polylactide by heteroselective initiators based on trivalent metals. Macromolecules 43:10201–10203. https://doi.org/10.1021/ma1025219
Choudhary A, Gandla D, Krow GR, Raines RT (2009) Nature of amide carbonyl–carbonyl interactions in proteins. J Am Chem Soc 131:7244–7246. https://doi.org/10.1021/ja901188y
Coffin RC, Diamanti SJ, Hotta A, Khanna V, Kramer EJ, Fredrickson GH, Bazan GC (2007) Pseudo-tetrablock copolymers with ethylene and a functionalized comonomer. Chem Commun. https://doi.org/10.1039/b705808j
Garlotta D (2001) A literature review of poly(lactic acid). J Polym Environ 9:63–84. https://doi.org/10.1023/a:1020200822435
Greiner A, Wendorff JH (2007) Electrospinning: a fascinating method for the preparation of ultrathin fibers. Angew Chem Int Ed Engl 46:5670–5703. https://doi.org/10.1002/anie.200604646
Hillmyer MA, Tolman WB (2014) Aliphatic polyester block polymers: renewable, degradable, and sustainable. Acc Chem Res 47:2390–2396. https://doi.org/10.1021/ar500121d
Hoshida T et al (2007) Controlling the adhesion between diamond-like carbon (DLC) film and high-density polyethylene (HDPE) substrate. Surf Coat Technol 202:1089–1093. https://doi.org/10.1016/j.surfcoat.2007.07.087
Inukai S, Kurokawa N, Hotta A (2018) Annealing and saponification of electrospun cellulose-acetate nanofibers used as reinforcement materials for composites. Compos Part A Appl Sci Manuf 113:158–165. https://doi.org/10.1016/j.compositesa.2018.07.028
Jordá-Vilaplana A, Fombuena V, García-García D, Samper MD, Sánchez-Nácher L (2014) Surface modification of polylactic acid (PLA) by air atmospheric plasma treatment. Eur Polym J 58:23–33. https://doi.org/10.1016/j.eurpolymj.2014.06.002
Kanemura C, Nakashima S, Hotta A (2012) Mechanical properties and chemical structures of biodegradable poly(butylene-succinate) for material reprocessing. Polym Degrad Stab 97:972–980. https://doi.org/10.1016/j.polymdegradstab.2012.03.015
Kontou E, Niaounakis M, Georgiopoulos P (2011) Comparative study of PLA nanocomposites reinforced with clay and silica nanofillers and their mixtures. J Appl Polym Sci 122:1519–1529. https://doi.org/10.1002/app.34234
Kontou E, Georgiopoulos P, Niaounakis M (2012) The role of nanofillers on the degradation behavior of polylactic acid. Polym Compos 33:282–294. https://doi.org/10.1002/pc.21258
Kurihara T, Isogai A (2013) Properties of poly(acrylamide)/TEMPO-oxidized cellulose nanofibril composite films. Cellulose 21:291–299. https://doi.org/10.1007/s10570-013-0124-z
Kurokawa N, Hotta A (2018) Thermomechanical properties of highly transparent self-reinforced polylactide composites with electrospun stereocomplex polylactide nanofibers. Polymer 153:214–222. https://doi.org/10.1016/j.polymer.2018.08.018
Kurokawa N, Kimura S, Hotta A (2017) Mechanical properties of poly(butylene succinate) composites with aligned cellulose-acetate nanofibers. J Appl Polym Sci 135:45429. https://doi.org/10.1002/app.45429
Liao H, Wu Y, Wu M, Zhan X, Liu H (2011) Aligned electrospun cellulose fibers reinforced epoxy resin composite films with high visible light transmittance. Cellulose 19:111–119. https://doi.org/10.1007/s10570-011-9604-1
Liu H, Hsieh Y-L (2002) Ultrafine fibrous cellulose membranes from electrospinning of cellulose acetate. J Polym Sci B Polym Phys 40:2119–2129. https://doi.org/10.1002/polb.10261
Maeda T, Takaesu K, Hotta A (2016) Syndiotactic polypropylene nanofibers obtained from solution electrospinning process at ambient temperature. J Appl Polym Sci 133:43238. https://doi.org/10.1002/app.43238
Martello MT, Schneiderman DK, Hillmyer MA (2014) Synthesis and melt processing of sustainable poly(ε-decalactone)-block-poly(lactide) multiblock thermoplastic elastomers. ACS Sustain Chem Eng 2:2519–2526. https://doi.org/10.1021/sc500412a
Miao C, Hamad WY (2013) Cellulose reinforced polymer composites and nanocomposites: a critical review. Cellulose 20:2221–2262. https://doi.org/10.1007/s10570-013-0007-3
Mizuno S, Maeda T, Kanemura C, Hotta A (2015) Biodegradability, reprocessability, and mechanical properties of polybutylene succinate (PBS) photografted by hydrophilic or hydrophobic membranes. Polym Degrad Stab 117:58–65. https://doi.org/10.1016/j.polymdegradstab.2015.03.015
Nakano A, Miki N, Hishida K, Hotta A (2012) Solution parameters for the fabrication of thinner silicone fibers by electrospinning. Phys Rev E: Stat Nonlinear Soft Matter Phys 86:011801. https://doi.org/10.1103/PhysRevE.86.011801
Nakayama Y, Aihara K, Yamanishi H, Fukuoka H, Tanaka R, Cai Z, Shiono T (2015) Synthesis of biodegradable thermoplastic elastomers fromε-caprolactone and lactide. J Polym Sci Part A Polym Chem 53:489–495. https://doi.org/10.1002/pola.27463
Neppalli R, Marega C, Marigo A, Bajgai MP, Kim HY, Causin V (2011) Improvement of tensile properties and tuning of the biodegradation behavior of polycaprolactone by addition of electrospun fibers. Polymer 52:4054–4060. https://doi.org/10.1016/j.polymer.2011.06.039
Neppalli R, Marega C, Marigo A, Bajgai MP, Kim HY, Ray SS, Causin V (2012) Electrospun nylon fibers for the improvement of mechanical properties and for the control of degradation behavior of poly(lactide)-based composites. J Mater Res 27:1399–1409. https://doi.org/10.1557/jmr.2012.70
Newberry RW, Raines RT (2013) n–>pi* interactions in poly(lactic acid) suggest a role in protein folding. Chem Commun (Camb) 49:7699–7701. https://doi.org/10.1039/c3cc44317e
Oishi Y, Nakaya M, Matsui E, Hotta A (2015) Structural and mechanical properties of cellulose composites made of isolated cellulose nanofibers and poly(vinyl alcohol). Compos Part A Appl Sci Manuf 73:72–79. https://doi.org/10.1016/j.compositesa.2015.02.026
Oksman K, Skrifvars M, Selin JF (2003) Natural fibres as reinforcement in polylactic acid (PLA) composites. Compos Sci Technol 63:1317–1324. https://doi.org/10.1016/s0266-3538(03)00103-9
Rahim A, Saha P, Jha KK, Sukumar N, Sarma BK (2017) Reciprocal carbonyl–carbonyl interactions in small molecules and proteins. Nat Commun 8:78. https://doi.org/10.1038/s41467-017-00081-x
Rasal RM, Janorkar AV, Hirt DE (2010) Poly(lactic acid) modifications. Prog Polym Sci 35:338–356. https://doi.org/10.1016/j.progpolymsci.2009.12.003
Siró I, Plackett D (2010) Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose 17:459–494. https://doi.org/10.1007/s10570-010-9405-y
Son WK, Youk JH, Lee TS, Park WH (2003) Electrospinning of ultrafine cellulose acetate fibers: studies of a new solvent system and deacetylation of ultrafine cellulose acetate fibers. J Polym Sci B Polym Phys 42:5–11. https://doi.org/10.1002/polb.10668
Tang C, Liu H (2008) Cellulose nanofiber reinforced poly(vinyl alcohol) composite film with high visible light transmittance. Compos Part A Appl Sci Manuf 39:1638–1643. https://doi.org/10.1016/j.compositesa.2008.07.005
Tang C, Wu M, Wu Y, Liu H (2011) Effects of fiber surface chemistry and size on the structure and properties of poly(vinyl alcohol) composite films reinforced with electrospun fibers. Compos Part A Appl Sci Manuf 42:1100–1109. https://doi.org/10.1016/j.compositesa.2011.04.015
Tashiro H, Nakaya M, Hotta A (2013) Enhancement of the gas barrier property of polymers by DLC coating with organosilane interlayer. Diam Relat Mater 35:7–13. https://doi.org/10.1016/j.diamond.2013.03.001
Tsubone D, Kodama H, Hasebe T, Hotta A (2007) Gas barrier properties and periodically fractured surface of thin DLC films coated on flexible polymer substrates. Surf Coat Technol 201:6431–6436. https://doi.org/10.1016/j.surfcoat.2006.12.009
Watts A, Kurokawa N, Hillmyer MA (2017) Strong, resilient, and sustainable aliphatic polyester thermoplastic elastomers. Biomacromolecules 18:1845–1854. https://doi.org/10.1021/acs.biomac.7b00283
Widiastuti I (2016) Polylactide nanocomposites for packaging materials: a review. AIP Conf Proc 1708:030020. https://doi.org/10.1063/1.4941486
Yano H, Sugiyama J, Nakagaito AN, Nogi M, Matsuura T, Hikita M, Handa K (2005) Optically transparent composites reinforced with networks of bacterial nanofibers. Adv Mater 17:153–155. https://doi.org/10.1002/adma.200400597
Zucchelli A, Focarete ML, Gualandi C, Ramakrishna S (2011) Electrospun nanofibers for enhancing structural performance of composite materials. Polym Adv Technol 22:339–349. https://doi.org/10.1002/pat.1837
Acknowledgments
This work was supported in part by Grant-in-Aid for Scientific Research (A) from the Japan Society for the Promotion of Science (JSPS: “KAKENHI”) (Nos. 15H02298 and 19H00831 to A.H.). It was also supported in part by MEXT Grant-in-Aid for the Program for Leading Graduate School (N.K.), and Grant-in-Aid for JSPS Research Fellow (No. 18J13281 to N.K).
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Kurokawa, N., Hotta, A. Regenerated cellulose nanofibers fabricated through electrospinning and saponification of cellulose acetate as reinforcement of polylactide composites. Cellulose 26, 7797–7808 (2019). https://doi.org/10.1007/s10570-019-02623-6
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DOI: https://doi.org/10.1007/s10570-019-02623-6