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Substitution of nanoclay in high gas barrier films of cellulose nanofibrils with cellulose nanocrystals and thermal treatment

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Abstract

The aim of this study is to design a nanocellulose based barrier film. For this purpose, cellulose nanofibrils (CNFs) are used as a matrix to create an entangled nanoporous network that is filled with two different nanofillers: nanoclay (reference), i.e. the mineral montmorillonite (MMT) and the bio-based TEMPO-oxidized cellulose nanocrystal (CNC-T), to produce different types of nanocelluloses and their main physical and chemical features were assessed. As expected, films based on neat CNFs exhibit good mechanical performance and excellent barrier properties at low moisture content. The introduction of 32.5 wt% of either nanofiller results in a significant improvement of barrier properties at high moisture content. Finally, thermal treatment of a dried CNF/CNC-T film results in a decrease of the oxygen permeability even at high moisture content (>70 %). This is mainly attributed to the hornification of nanocellulose. A key result of this study is that the oxygen permeability of an all-nanocellulose film in 85 % relative humidity (RH), is similar to CNF film with mineral nanoclay (MMT), i.e. 2.1 instead of 1.7 cm3 µm m−2 day−1 kPa−1, respectively.

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References

  • Alexandrescu L, Syverud K, Gatti A, Chinga-Carrasco G (2013) Cytotoxicity tests of cellulose nanofibril-based structures. Cellulose 20:1765–1775

    Article  CAS  Google Scholar 

  • Araki J, Wada M, Kuga S, Okano T (1999) Influence of surface charge on viscosity behavior of cellulose microcrystal suspension. J Wood Sci 45:258–261

    Article  CAS  Google Scholar 

  • Atalla RH, VanderHart DL (1999) The role of solid state 13C NMR spectroscopy in studies of the nature of native celluloses. Solid State Nucl Magn Reson 15:1–19

    Article  CAS  Google Scholar 

  • Aulin C, Gällstedt M, Lindström T (2010) Oxygen and oil barrier properties of microfibrillated cellulose films and coatings. Cellulose 17:559–574

    Article  CAS  Google Scholar 

  • 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 4:6622–6628

    Article  CAS  Google Scholar 

  • Bergenstråhle M, Berglund LA, Mazeau K (2007) Thermal response in crystalline Iβ cellulose: a molecular dynamics study. J Phys Chem B 111:9138–9145

    Article  Google Scholar 

  • Chauve G, Bras J (2014) Industrial point of view of nanocellulose materials and their possible applications. In: Oksman K (ed) Handbook of Green Materials. World Scientific, pp 233–252

  • Chinga-Carrasco G (2011) Cellulose fibres, nanofibrils and microfibrils: The morphological sequence of MFC components from a plant physiology and fibre technology point of view. Nanoscale Res Lett 6

  • Fukuzumi H, Saito T, Iwata T, Kumamoto Y, Isogai A (2008) Transparent and high gas barrier films of cellulose nanofibers prepared by TEMPO-mediated oxidation. Biomacromolecules 10:162–165

    Article  Google Scholar 

  • Fukuzumi H, Saito T, Okita Y, Isogai A (2010) Thermal stabilization of TEMPO-oxidized cellulose. Polym Degrad Stab 95:1502–1508

    Article  CAS  Google Scholar 

  • Guilbert S, Guillaume C, Gontard N (2011) New packaging materials based on renewable resources: properties, applications, and prospects. In: Aguilera JM, Simpson R, Welti-Chanes J, Bermudez-Aguirre D, Barbosa-Canovas G (eds) Food engineering interfaces. Food engineering series. Springer, New York, pp 619–630

    Google Scholar 

  • Habibi Y (2014) Key advances in the chemical modification of nanocelluloses. Chem Soc Rev 43:1519–1542

    Article  CAS  Google Scholar 

  • Habibi Y, Chanzy H, Vignon MR (2006) TEMPO-mediated surface oxidation of cellulose whiskers. Cellulose 13:679–687

    Article  CAS  Google Scholar 

  • Ho TTT, Zimmermann T, Ohr S, Caseri WR (2012) Composites of cationic nanofibrillated cellulose and layered silicates: water vapor barrier and mechanical properties. ACS Appl Mater Interfaces 4:4832–4840

    Article  CAS  Google Scholar 

  • Hua K, Carlsson DO, Alander E, Lindstrom T, Stromme M, Mihranyan A, Ferraz N (2014) Translational study between structure and biological response of nanocellulose from wood and green algae. RSC Advances 4:2892–2903

    Article  CAS  Google Scholar 

  • Iwamoto S, Abe K, Yano H (2008) The effect of hemicelluloses on wood pulp nanofibrillation and nanofiber network characteristics. Biomacromolecules 9:1022–1026

    Article  CAS  Google Scholar 

  • Johansson C et al (2012) Renewable fibers and bio-based materials for packaging applications—a review of recent developments. Bioresources 7:2506–2552

    Article  Google Scholar 

  • Lavoine N, Desloges I, Dufresne A, Bras J (2012) Microfibrillated cellulose—its barrier properties and applications in cellulosic materials: a review. Carbohydr Polym 90:735–764

    Article  CAS  Google Scholar 

  • Liu A, Berglund LA (2012) Clay nanopaper composites of nacre-like structure based on montmorrilonite and cellulose nanofibers—improvements due to chitosan addition. Carbohydr Polym 87:53–60

    Article  CAS  Google Scholar 

  • Liu A, Berglund LA (2013) Fire-retardant and ductile clay nanopaper biocomposites based on montmorillonite in matrix of cellulose nanofibers and carboxymethyl cellulose. Eur Polym J 49:940–949

    Article  CAS  Google Scholar 

  • Minelli M, Baschetti MG, Doghieri F, Ankerfors M, Lindstrom T, Siro I, Plackett D (2010) Investigation of mass transport properties of microfibrillated cellulose (MFC) films. J Memb Sci 358:67–75

    Article  CAS  Google Scholar 

  • Montanari S, Roumani M, Heux L, Vignon MR (2005) Topochemistry of carboxylated cellulose nanocrystals resulting from TEMPO-mediated oxidation. Macromolecules 38:1665–1671

    Article  CAS  Google Scholar 

  • Österberg M, Vartiainen J, Lucenius J, Hippi U, Seppälä J, Serimaa R, Laine J (2013) A fast method to produce strong NFC films as a platform for barrier and functional materials. ACS Appl Mater Interfaces 5:4640–4647

    Article  Google Scholar 

  • Pääkkö M et al (2007) Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels. Biomacromolecules 8:1934–1941

    Article  Google Scholar 

  • Pitkänen M, Kangas H, Vartiainen J (2014) Toxicity and Health Issues. In: Oksman K (ed) Handbook of green materials. World Scientific, pp 181–205

  • Plackett D, Anturi H, Hedenqvist M, Ankerfors M, Gallstedt M, Lindstrom T, Siro I (2010) Physical properties and morphology of films prepared from microfibrillated cellulose and microfibrillated cellulose in combination with amylopectin. J Appl Polym Sci 117:3601–3609

    CAS  Google Scholar 

  • Reddy N, Yang Y (2010) Citric acid cross-linking of starch films. Food Chem 118:702–711

    Article  CAS  Google Scholar 

  • Rodionova G, Lenes M, Eriksen Ø, Gregersen Ø (2011) Surface chemical modification of microfibrillated cellulose: improvement of barrier properties for packaging applications. Cellulose 18:127–134

    Article  CAS  Google Scholar 

  • Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8:2485–2491

    Article  CAS  Google Scholar 

  • Segal L, Creely JJ, Martin AE Jr, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Sharma S, Zhang X, Nair SS, Ragauskas A, Zhu J, Deng Y (2014) Thermally enhanced high performance cellulose nano fibril barrier membranes. RSC Advances 4:45136–45142

    Article  CAS  Google Scholar 

  • Shinoda R, Saito T, Okita Y, Isogai A (2012) Relationship between length and degree of polymerization of TEMPO-oxidized cellulose nanofibrils. Biomacromolecules 13:842–849

    Article  CAS  Google Scholar 

  • Siqueira G, Bras J, Dufresne A (2010) Luffa cylindrica as a lignocellulosic source of fiber, microfibrillated cellulose, and cellulose nanocrystals. Bioresources 5:727–740

    CAS  Google Scholar 

  • Siró I, Plackett D (2010) Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose 17:459–494

    Article  Google Scholar 

  • Spence KL, Venditti RA, Habibi Y, Rojas OJ, Pawlak JJ (2010) The effect of chemical composition on microfibrillar cellulose films from wood pulps: mechanical processing and physical properties. Bioresour Technol 101:5961–5968

    Article  CAS  Google Scholar 

  • Spoljaric S, Salminen A, Luong ND, Seppälä J (2013) Crosslinked nanofibrillated cellulose: poly (acrylic acid) nanocomposite films; enhanced mechanical performance in aqueous environments. Cellulose 20:2991–3005

    Article  CAS  Google Scholar 

  • Syverud K, Stenius P (2009) Strength and barrier properties of MFC films. Cellulose 16:75–85

    Article  CAS  Google Scholar 

  • Syverud K, Chinga-Carrasco G, Toledo J, Toledo PG (2011) A comparative study of Eucalyptus and Pinus radiata pulp fibres as raw materials for production of cellulose nanofibrils. Carbohydr Polym 84:1033–1038

    Article  CAS  Google Scholar 

  • Tang XZ, Kumar P, Alavi S, Sandeep KP (2011) Recent advances in biopolymers and biopolymer-based nanocomposites for food packaging materials. Crit Rev Food Sci Nutr 52:426–442

    Article  Google Scholar 

  • Tingaut P, Zimmermann T, Lopez-Suevos F (2009) Synthesis and characterization of bionanocomposites with tunable properties from poly(lactic acid) and acetylated microfibrillated cellulose. Biomacromolecules 11:454–464

    Article  Google Scholar 

  • Wu CN, Saito T, Fujisawa S, Fukuzumi H, Isogai A (2012) Ultrastrong and high gas-barrier nanocellulose/clay-layered composites. Biomacromolecules 13:1927–1932

    Article  CAS  Google Scholar 

  • Yang CQ, Wang X, Kang I-S (1997) Ester crosslinking of cotton fabric by polymeric carboxylic acids and citric acid. Text Res J 67:334–342

    CAS  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge Papeteries du Léman, and the French National Research Agency (ANRT) for financial and material support for the PhD thesis. TekLiCell cluster and region Rhone-Alpes are acknowledged for their financial support to the experimental setups. We would like to thank Francine Roussel (Grenoble Institute of Technology) for her expertise in providing SEM imaging and Stéphane Coindeau for performing XRD analysis. LGP2 is part of the LabEx Tec 21 (Investissements d’Avenir Grant Agreement No. ANR-11-LABX-0030) and of the Energies du Future and PolyNat Carnot Institutes. The OTR measurements have been supported by the PFI project NORCEL: The Norwegian Nanocellulose Technology Platform, funded by the Research Council of Norway.

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Correspondence to Julien Bras.

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Bardet, R., Reverdy, C., Belgacem, N. et al. Substitution of nanoclay in high gas barrier films of cellulose nanofibrils with cellulose nanocrystals and thermal treatment. Cellulose 22, 1227–1241 (2015). https://doi.org/10.1007/s10570-015-0547-9

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  • DOI: https://doi.org/10.1007/s10570-015-0547-9

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