Abstract
Preparation of cellulose nanofibril (CNF)-reinforced, biodegradable polymer composites is challenging in that it’s hard to achieve good dispersion of the hydrophilic cellulose fibers in a hydrophobic polymer matrix. In this work, we developed a surfactant-free and efficient process to prepare CNF-reinforced poly (lactic acid) (PLA) composites from an aqueous dichloromethane Pickering emulsion self-emulsified by CNFs. CNF/PLA composites of homogeneous dispersion were obtained upon evaporation of CH2Cl2, filtration, drying and hot-pressing. Differential scanning calorimetry measurement revealed an enhanced crystallization capacity of the CNF/PLA composites. Thermogravimetric analysis indicated an increase of onset degradation temperature. The composites displayed an enhanced storage modulus compared with neat PLA throughout the testing temperature range, and especially in the high-temperature region (>70 °C). Enhancements of the flexural modulus and strength were also achieved.
Similar content being viewed by others
References
Almasi H, Ghanbarzadeh B, Dehghannya J, Entezami AA, Asl AK (2015) Novel nanocomposites based on fatty acid modified cellulose nanofibers/poly (lactic acid): morphological and physical properties. Food Packag Shelf Life 5:21–31. doi:10.1016/j.fpsl.2015.04.003
Angles MN, Dufresne A (2001) Plasticized starch/tunicin whiskers nanocomposite materials. 2. Mechanical behavior. Macromolecules 34:2921–2931
Avendano C, Brun N, Fontaine O, In M, Mehdi A, Stocco A, Vioux A (2016) Multiwalled carbon nanotube/cellulose composite: from aqueous dispersions to Pickering emulsions. Langmuir 32:3907–3916
Awal A, Rana M, Sain M (2015) Thermorheological and mechanical properties of cellulose reinforced PLA bio-composites. Mech Mater 80(Part A):87–95
Azizi Samir MAS, Alloin F, Sanchez J-Y, El Kissi N, Dufresne A (2004) Preparation of cellulose whiskers reinforced nanocomposites from an organic medium suspension. Macromolecules 37:1386–1393
Capron I, Cathala B (2013) Surfactant-free high internal phase emulsions stabilized by cellulose nanocrystals. Biomacromol 14:291–296
Cherhal F, Cousin F, Capron I (2016) Structural description of the interface of Pickering emulsions stabilized by cellulose nanocrystals. Biomacromol 17:496–502
Cunha AG, Mougel J-B, Cathala B, Berglund LA, Capron I (2014) Preparation of double Pickering emulsions stabilized by chemically tailored nanocelluloses. Langmuir 30:9327–9335
de Menezes AJ, Siqueira G, Curvelo AA, Dufresne A (2009) Extrusion and characterization of functionalized cellulose whiskers reinforced polyethylene nanocomposites. Polymer 50:4552–4563
Goffin A-L, Raquez J-M, Duquesne E, Siqueira G, Habibi Y, Dufresne A, Dubois P (2011) From interfacial ring-opening polymerization to melt processing of cellulose nanowhisker-filled polylactide-based nanocomposites. Biomacromol 12:2456–2465
Habibi Y (2014) Key advances in the chemical modification of nanocelluloses. Chem Soc Rev 43:1519–1542
Hasani M, Cranston ED, Westman G, Gray DG (2008) Cationic surface functionalization of cellulose nanocrystals. Soft Matter 4:2238–2244
Hu Z, Ballinger S, Pelton R, Cranston ED (2015) Surfactant-enhanced cellulose nanocrystal Pickering emulsions. J Colloid Interface Sci 439:139–148
Hu Z, Marway HS, Kasem H, Pelton R, Cranston ED (2016) Dried and redispersible cellulose nanocrystal Pickering emulsions. ACS Macro Lett 5:185–189
Iwatake A, Nogi M, Yano H (2008) Cellulose nanofiber-reinforced polylactic acid. Compos Sci Technol 68:2103–2106
Jonoobi M, Harun J, Mathew AP, Oksman K (2010) Mechanical properties of cellulose nanofiber (CNF) reinforced polylactic acid (PLA) prepared by twin screw extrusion. Compos Sci Technol 70:1742–1747
Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed 50:5438–5466
Kose R, Kondo T (2013) Size effects of cellulose nanofibers for enhancing the crystallization of poly (lactic acid). J Appl Polym Sci 128:1200–1205
Kvien I, Tanem BS, Oksman K (2005) Characterization of cellulose whiskers and their nanocomposites by atomic force and electron microscopy. Biomacromol 6:3160–3165
Larsson K, Berglund LA, Ankerfors M, Lindström T (2012) Polylactide latex/nanofibrillated cellulose bionanocomposites of high nanofibrillated cellulose content and nanopaper network structure prepared by a papermaking route. J Appl Polym Sci 125:2460–2466
Lee K-Y, Quero F, Blaker JJ, Hill CA, Eichhorn SJ, Bismarck A (2011) Surface only modification of bacterial cellulose nanofibres with organic acids. Cellulose 18:595–605
Lee K-Y, Aitomäki Y, Berglund LA, Oksman K, Bismarck A (2014) On the use of nanocellulose as reinforcement in polymer matrix composites. Compos Sci Technol 105:15–27
Mariano M, El Kissi N, Dufresne A (2014) Cellulose nanocrystals and related nanocomposites: review of some properties and challenges. J Polym Sci B: Polym Phys 52:791–806
Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994
Nakagaito AN, Fujimura A, Sakai T, Hama Y, Yano H (2009) Production of microfibrillated cellulose (MFC)-reinforced polylactic acid (PLA) nanocomposites from sheets obtained by a papermaking-like process. Compos Sci Technol 69:1293–1297
Nypelö T, Rodriguez-Abreu C, Kolen’ko YV, Rivas J, Rojas OJ (2014) Microbeads and hollow microcapsules obtained by self-assembly of Pickering magneto-responsive cellulose nanocrystals. ACS Appl Mater Interfaces 6:16851–16858
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
Pandey JK, Nakagaito AN, Takagi H (2013) Fabrication and applications of cellulose nanoparticle-based polymer composites. Polym Eng Sci 53:1–8
Perinović S, Andričić B, Erceg M (2010) Thermal properties of poly (l-lactide)/olive stone flour composites. Thermochim Acta 510:97–102
Petersson L, Oksman K (2006) Biopolymer based nanocomposites: comparing layered silicates and microcrystalline cellulose as nanoreinforcement. Compos Sci Technol 66:2187–2196
Raquez J-M, Murena Y, Goffin A-L, Habibi Y, Ruelle B, DeBuyl F, Dubois P (2012) Surface-modification of cellulose nanowhiskers and their use as nanoreinforcers into polylactide: a sustainably-integrated approach. Compos Sci Technol 72:544–549
Raquez J-M, Habibi Y, Murariu M, Dubois P (2013) Polylactide (PLA)-based nanocomposites. Prog Polym Sci 38:1504–1542
Robles E, Urruzola I, Labidi J, Serrano L (2015) Surface-modified nano-cellulose as reinforcement in poly (lactic acid) to conform new composites. Ind Crops Prod 71:44–53
Saeidlou S, Huneault MA, Li H, Park CB (2012) Poly (lactic acid) crystallization. Prog Polym Sci 37:1657–1677
Scaffaro R, Botta L, Lopresti F, Maio A, Sutera F (2017) Polysaccharide nanocrystals as fillers for PLA based nanocomposites. Cellulose 24:447–448
Siqueira G, Bras J, Dufresne A (2008) Cellulose whiskers versus microfibrils: influence of the nature of the nanoparticle and its surface functionalization on the thermal and mechanical properties of nanocomposites. Biomacromol 10:425–432
Song Y, Tashiro K, Xu D, Liu J, Bin Y (2013) Crystallization behavior of poly (lactic acid)/microfibrillated cellulose composite. Polymer 54:3417–3425
Spinella S et al (2015) Polylactide/cellulose nanocrystal nanocomposites: efficient routes for nanofiber modification and effects of nanofiber chemistry on PLA reinforcement. Polymer 65:9–17
Suryanegara L, Nakagaito AN, Yano H (2009) The effect of crystallization of PLA on the thermal and mechanical properties of microfibrillated cellulose-reinforced PLA composites. Compos Sci Technol 69:1187–1192
Suryanegara L, Nakagaito AN, Yano H (2010) Thermo-mechanical properties of microfibrillated cellulose-reinforced partially crystallized PLA composites. Cellulose 17:771–778
Wang T, Drzal LT (2012) Cellulose-nanofiber-reinforced poly (lactic acid) composites prepared by a water-based approach. ACS Appl Mater Interfaces 4:5079–5085
Yuan H, Nishiyama Y, Wada M, Kuga S (2006) Surface acylation of cellulose whiskers by drying aqueous emulsion. Biomacromol 7:696–700
Zhu Y, Zheng Y, Zong L, Wang F, Wang A (2016) Fabrication of magnetic hydroxypropyl cellulose-g-poly (acrylic acid) porous spheres via Pickering high internal phase emulsion for removal of Cu2+ and Cd2+. Carbohydr Polym 149:242–250
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (No. 51403035), Programme of Introducing Talents of Discipline to Universities (No. 105-07-005735) and the Fundamental Research Funds for the Central Universities (No. 15D110510).
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Zhang, Y., Wu, J., Wang, B. et al. Cellulose nanofibril-reinforced biodegradable polymer composites obtained via a Pickering emulsion approach. Cellulose 24, 3313–3322 (2017). https://doi.org/10.1007/s10570-017-1324-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-017-1324-8