Skip to main content
SpringerLink
Log in

Multi-functional coating of cellulose nanocrystals for flexible packaging applications

  • Original Paper
  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

In this paper, we systematically address the performance of cellulose nanocrystals (CNs) coated flexible food packaging films. Firstly, the morphology of CNs from cotton linters and homogeneity of its coating on different substrates were characterized by transmission electronic microscopy and atomic force microscopy. Then, the 1.5 μm thick CNs coating on polyethylene terephthalate (PET), oriented polypropylene, oriented polyamide (OPA), and cellophane films were characterized for their mechanical, optical, anti-fog, and barrier properties. CNs coating reduces the coefficient of friction while maintaining high transparency (~90 %) and low haze (3–4 %) values, and shows excellent anti-fog properties and remarkable oxygen barrier (oxygen permeability coefficient of CNs coating, P’O2, 0.003 cm3 μm m−2 24 h−1 kPa−1). In addition, the Gelbo flex test combined with oxygen permeance (PO2) measurements and optical microscopy are firstly reported for evaluating the durability of coatings, revealing that the CNs coated PET and OPA provide the best performance among the investigated coated films. CNs are therefore considered to be a promising multi-functional coating for flexible food packaging.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  • Angles MN, Dufresne A (2000) Plasticized starch/tunicin whiskers nanocomposites. 1. Structural analysis. Macromolecules 33:8344–8353

    Article  CAS  Google Scholar 

  • Aulin C, Ahola S, Josefsson P, Nishino T, Hirose Y, Österberg M et al (2009) Nanoscale cellulose films with different crystallinities and mesostructures—their surface properties and interaction with water. Langmuir 25:7675–7685

    Article  CAS  Google Scholar 

  • Auras R, Harte B, Selke S (2004) An overview of polylactides as packaging materials. Macromol Biosci 4:835–864

    Article  CAS  Google Scholar 

  • Avella M, De Vlieger JJ, Errico ME, Fischer S, Vacca P, Volpe MG (2005) Biodegradable starch/clay nanocomposite films for food packaging applications. Food Chem 93:467–474

    Article  CAS  Google Scholar 

  • Belbekhouche S, Bras J, Siqueira G, Chappey C, Lebrun L, Khelifi B et al (2011) Water sorption behavior and gas barrier properties of cellulose whiskers and microfibrils films. Carbohydr Polym 83:1740–1748

    Article  CAS  Google Scholar 

  • Briscoe BJ, Galvin KP (1991) The effect of surface fog on the transmittance of light. Sol Energy 46:191–197

    Article  Google Scholar 

  • Cerclier C, Cousin F, Bizot H, Moreau C, Cathala B (2010) Elaboration of spin-coated cellulose-xyloglucan multilayered thin films. Langmuir 26:17248–17255

    Article  CAS  Google Scholar 

  • Cha DS, Chinnan MS (2004) Biopolymer-based antimicrobial packaging: a review. Crit Rev Food Sci Nutr 44:223–237

    Article  CAS  Google Scholar 

  • Chatham H (1996) Oxygen diffusion barrier properties of transparent oxide coatings on polymeric substrates. Surf Coat Technol 78:1–9

    Article  CAS  Google Scholar 

  • Cranston ED, Gray DG (2008) Birefringence in spin-coated films containing cellulose nanocrystals. Colloids Surf a-Physicochem Eng Aspects 325:44–51

    Article  CAS  Google Scholar 

  • Creatore M, Palumbo F, d’Agostino R (2002) Deposition of SiOx films from hexamethyldisiloxane/oxygen radiofrequency glow discharges: process optimization by plasma diagnostics. Plasmas Polym 7:291–310

    Article  CAS  Google Scholar 

  • da Silva JBA, Pereira FV, Druzian JI (2012) Cassava starch-based films plasticized with sucrose and inverted sugar and reinforced with cellulose nanocrystals. J Food Sci 77:N14–N19

    Article  Google Scholar 

  • Dankovich TA, Gray DG (2011) Contact angle measurements on smooth nanocrystalline cellulose (I) thin films. J Adhes Sci Technol 25:699–708

    Article  CAS  Google Scholar 

  • de Mesquita JP, Donnici CL, Pereira FV (2010) Biobased nanocomposites from layer-by-layer assembly of cellulose nanowhiskers with chitosan. Biomacromolecules 11:473–480

    Article  Google Scholar 

  • Dong H, Strawhecker KE, Snyder JF, Orlicki JA, Reiner RS, Rudie AW (2012) Cellulose nanocrystals as a reinforcing material for electrospun poly(methyl methacrylate) fibers: formation, properties and nanomechanical characterization. Carbohydr Polym 87:2488–2495

    Article  CAS  Google Scholar 

  • Drumright RE, Gruber PR, Henton DE (2000) Polylactic acid technology. Adv Mater 12:1841–1846

    Article  CAS  Google Scholar 

  • Elazzouzi-Hafraoui S, Nishiyama Y, Putaux J-L, Heux L, Dubreuil F, Rochas C (2007) The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose. Biomacromolecules 9:57–65

    Article  Google Scholar 

  • Erlat AG, Spontak RJ, Clarke RP, Robinson TC, Haaland PD, Tropsha Y et al (1999) SiOx gas barrier coatings on polymer substrates: morphology and gas transport considerations. J Phys Chem B 103:6047–6055

    Article  CAS  Google Scholar 

  • Farris S, Introzzi L, Piergiovanni L (2009) Evaluation of a bio-coating as a solution to improve barrier, friction and optical properties of plastic films. Packag Technol Sci 22:69–83

    Article  CAS  Google Scholar 

  • Farris S, Introzzi L, Fuentes-Alventosa JM, Santo N, Rocca R, Piergiovanni L (2012) Self-assembled pullulan-silica oxygen barrier hybrid coatings for food packaging applications. J Agric Food Chem 60:782–790

    Article  CAS  Google Scholar 

  • Fortunati E, Peltzer M, Armentano I, Torre L, Jimenez A, Kenny JM (2012) Effects of modified cellulose nanocrystals on the barrier and migration properties of PLA nano-biocomposites. Carbohydr Polym 90:948–956

    Article  CAS  Google Scholar 

  • Fujisawa S, Okita Y, Fukuzumi H, Saito T, Isogai A (2011) Preparation and characterization of TEMPO-oxidized cellulose nanofibril films with free carboxyl groups. Carbohydr Polym 84:579–583

    Article  CAS  Google Scholar 

  • Fukuzumi H, Saito T, Wata T, Kumamoto Y, Isogai A (2009) Transparent and high gas barrier films of cellulose nanofibers prepared by TEMPO-mediated oxidation. Biomacromolecules 10:162–165

    Article  CAS  Google Scholar 

  • Fukuzumi H, Saito T, Iwamoto S, Kumamoto Y, Ohdaira T, Suzuki R et al (2011) Pore size determination of TEMPO-oxidized cellulose nanofibril films by positron annihilation lifetime spectroscopy. Biomacromolecules 12:4057–4062

    Article  CAS  Google Scholar 

  • Fukuzumi H, Saito T, Isogai A (2012) Influence of TEMPO-oxidized cellulose nanofibril length on film properties. Carbohydr Polym. doi:10.1016/j.carbpol.2012.04.069

  • Ghasemi H, Carreau PJ, Kamal MR, Tabatabaei SH (2012) Properties of PET/clay nanocomposite films. Polym Eng Sci 52:420–430

    Article  CAS  Google Scholar 

  • Goffin AL, Raquez JM, Duquesne E, Siqueira G, Habibi Y, Dufresne A et al (2011) From interfacial ring-opening polymerization to melt processing of cellulose nanowhisker-filled polylactide-based nanocomposites. Biomacromolecules 12:2456–2465

    Article  CAS  Google Scholar 

  • Guillaume C, Pinte J, Gontard N, Gastaldi E (2010) Wheat gluten-coated papers for bio-based food packaging: structure, surface and transfer properties. Food Res Int 43:1395–1401

    Article  CAS  Google Scholar 

  • Haas KH, Amberg-Schwab S, Rose K, Schottner G (1999) Functionalized coatings based on inorganic-organic polymers (ORMOCER (R) s) and their combination with vapor deposited inorganic thin films. Surf Coat Technol 111:72–79

    Article  CAS  Google Scholar 

  • Habibi Y, Goffin AL, Schiltz N, Duquesne E, Dubois P, Dufresne A (2008) Bionanocomposites based on poly(epsilon-caprolactone)-grafted cellulose nanocrystals by ring-opening polymerization. J Mater Chem 18:5002–5010

    Article  CAS  Google Scholar 

  • Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110:3479–3500

    Article  CAS  Google Scholar 

  • Hansen NML, Plackett D (2008) Sustainable films and coatings from hemicelluloses: a review. Biomacromolecules 9:1493–1505

    Article  CAS  Google Scholar 

  • Hoeger I, Rojas OJ, Efimenko K, Velev OD, Kelley SS (2011) Ultrathin film coatings of aligned cellulose nanocrystals from a convective-shear assembly system and their surface mechanical properties. Soft Matter 7:1957–1967

    Article  CAS  Google Scholar 

  • Howarter JA, Youngblood JP (2008) Self-cleaning and next generation anti-fog surfaces and coatings. Macromol Rapid Commun 29:455–466

    Article  CAS  Google Scholar 

  • Hult EL, Iotti M, Lenes M (2010) Efficient approach to high barrier packaging using microfibrillar cellulose and shellac. Cellulose 17:575–586

    Article  CAS  Google Scholar 

  • Introzzi L, Fuentes-Alventosa JM, Cozzolino CA, Trabattoni S, Tavazzi S, Bianchi CL et al (2012) “Wetting Enhancer” pullulan coating for antifog packaging applications. ACS Appl Mater Interfaces 4:3692–3700

    Article  CAS  Google Scholar 

  • Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85

    Article  CAS  Google Scholar 

  • Jang W-S, Rawson I, Grunlan JC (2008) Layer-by-layer assembly of thin film oxygen barrier. Thin Solid Films 516:4819–4825

    Article  CAS  Google Scholar 

  • Kato Y, Kaminaga J, Matsuo R, Isogai A (2005) Oxygen permeability and biodegradability of polyuronic acids prepared from polysaccharides by TEMPO-mediated oxidation. J Polym Environ 13:261–266

    Article  CAS  Google Scholar 

  • Kontturi E, Johansson LS, Kontturi KS, Ahonen P, Thune PC, Laine J (2007) Cellulose nanocrystal submonolayers by spin coating. Langmuir 23:9674–9680

    Article  CAS  Google Scholar 

  • Krikorian V, Pochan DJ (2003) Poly (l-lactic acid)/layered silicate nanocomposite: fabrication, characterization, and properties. Chem Mater 15:4317–4324

    Article  CAS  Google Scholar 

  • Lange J, Wyser Y (2003) Recent innovations in barrier technologies for plastic packaging—a review. Packag Technol Sci 16:149–158

    Article  CAS  Google Scholar 

  • Lee DS, Yam KL, Piergiovanni L (2008) Chapter 4: Permeation of gas and vapor. In: Food packaging science and technology. CRC Press–Taylor & Francis Group, Boca Raton, London, New York, pp 58–59, 86–93

  • Li B, Logan BE (2004) Bacterial adhesion to glass and metal-oxide surfaces. Colloids Surf B 36:81–90

    Article  CAS  Google Scholar 

  • Li F, Biagioni P, Finazzi M, Tavazzi S, Piergiovanni L (2013) Tunable green oxygen barrier through layer-by-layer self-assembly of chitosan and cellulose nanocrystals. Carbohydr Polym 92:2128–2134

    Article  CAS  Google Scholar 

  • Lim LT, Auras R, Rubino M (2008) Processing technologies for poly(lactic acid). Prog Polym Sci 33:820–852

    Article  CAS  Google Scholar 

  • Lordan S, Kennedy JE, Higginbotham CL (2011) Cytotoxic effects induced by unmodified and organically modified nanoclays in the human hepatic HepG2 cell line. J Appl Toxicol 31:27–35

    Article  CAS  Google Scholar 

  • Martinez-Sanz M, Lopez Rubio A, Lagaron JM (2012) On the optimization of the dispersion of unmodified bacterial cellulose nanowhiskers into polylactide via melt compounding to significantly enhance barrier and mechanical properties. Biomacromolecules 13:3887–3899

    Google Scholar 

  • Mazeau K, Heux L (2003) Molecular dynamics simulations of bulk native crystalline and amorphous structures of cellulose. J Phys Chem B 107:2394–2403

    Article  CAS  Google Scholar 

  • Montaño-Leyva B, Ghizzi D, da Silva G, Gastaldi E, Torres-Chávez P, Gontard N, Angellier-Coussy H (2013) Biocomposites from wheat proteins and fibers: structure/mechanical properties relationships. Ind Crops Prod 43:545–555

    Article  Google Scholar 

  • Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994

    Article  CAS  Google Scholar 

  • Muzzarelli RAA, Boudrant J, Meyer D, Manno N, DeMarchis M, Paoletti MG (2012) Current views on fungal chitin/chitosan, human chitinases, food preservation, glucans, pectins and inulin: a tribute to Henri Braconnot, precursor of the carbohydrate polymers science, on the chitin bicentennial. Carbohydr Polym 87:995–1012

    Article  CAS  Google Scholar 

  • No HK, Meyers SP, Prinyawiwatkul W, Xu Z (2007) Applications of chitosan for improvement of quality and shelf life of foods: a review. J Food Sci 72:R87–R100

    Article  CAS  Google Scholar 

  • Noorani S, Simonsen J, Atre S (2007) Nano-enabled microtechnology: polysulfone nanocomposites incorporating cellulose nanocrystals. Cellulose 14:577–584

    Article  CAS  Google Scholar 

  • Nuraje N, Asmatulu R, Cohen RE, Rubner MF (2010) Durable antifog films from layer-by-layer molecularly blended hydrophilic polysaccharides. Langmuir 27:782–791

    Article  Google Scholar 

  • Priolo MA, Gamboa D, Holder KM, Grunlan JC (2010) Super gas barrier of transparent polymer–clay multilayer ultrathin films. Nano Lett 10:4970–4974

    Article  CAS  Google Scholar 

  • Ray SS, Yamada K, Okamoto M, Ueda K (2002) Polylactide-layered silicate nanocomposite: a novel biodegradable material. Nano Lett 2:1093–1096

    Article  CAS  Google Scholar 

  • Ray SS, Yamada K, Okamoto M, Ueda K (2003) New polylactide-layered silicate nanocomposites. 2. Concurrent improvements of material properties, biodegradability and melt rheology. Polymer 44:857–866

    Article  Google Scholar 

  • Rhim J-W, Ng PKW (2007) Natural biopolymer-based nanocomposite films for packaging applications. Crit Rev Food Sci Nutr 47:411–433

    Article  CAS  Google Scholar 

  • Ringus DL, Moraru CI (2013) Pulsed Ligh inactivation of Listeria innocua on food packaging materials of different surface roughness and reflectivity. J Food Eng 114:331–337

    Article  Google Scholar 

  • Rodionova G, Saito T, Lenes M, Eriksen O, Gregersen O, Fukuzumi H et al (2012) Mechanical and oxygen barrier properties of films prepared from fibrillated dispersions of TEMPO-oxidized Norway spruce and Eucalyptus pulps. Cellulose 19:705–711

    Article  CAS  Google Scholar 

  • Sanchez-Garcia MD, Hilliou L, Lagaron JM (2010) Morphology and water barrier properties of nanobiocomposites of k/i-hybrid carrageenan and cellulose nanowhiskers. J Agric Food Chem 58:12847–12857

    Article  CAS  Google Scholar 

  • Sánchez-Valdes S, López-Quintanilla ML, Ramírez-Vargas E, Medellín-Rodríguez FJ, Gutierrez-Rodriguez JM (2006) Effect of ionomeric compatibilizer on clay dispersion in polyethylene/clay nanocomposites. Macromol Mater Eng 291:128–136

    Article  Google Scholar 

  • Shellenberger K, Logan BE (2001) Effect of molecular scale roughness of glass beads on colloidal and bacterial deposition. Environ Sci Technol 36:184–189

    Article  Google Scholar 

  • Siqueira G, Abdillahi H, Bras J, Dufresne A (2010) High reinforcing capability cellulose nanocrystals extracted from Syngonanthus nitens (Capim Dourado). Cellulose 17:289–298

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  • Svagan AJ, Åkesson A, Cárdenas M, Bulut S, Knudsen JC, Risbo J et al (2012) Transparent films based on PLA and montmorillonite with tunable oxygen barrier properties. Biomacromolecules 13:397–405

    Article  CAS  Google Scholar 

  • Tharanathan RN (2003) Biodegradable films and composite coatings: past, present and future. Trends Food Sci Technol 14:71–78

    Article  CAS  Google Scholar 

  • van Oss CJ (2003) Long-range and short-range mechanisms of hydrophobic attraction and hydrophilic repulsion in specific and aspecific interactions. J Mol Recognit 16:177–190

    Article  Google Scholar 

  • van Oss CJ (2006) In: Dekker M (ed) Interfacial forces in aqueous media. CRC Press, New York, pp 18–28, 93–107

  • Vert M, Schwarch G, Coudane J (1995) Present and future of PLA polymers. J Macromol Sci-Pure Appl Chem A32:787–796

    CAS  Google Scholar 

  • Yang Y-H, Haile M, Park YT, Malek FA, Grunlan JC (2011) Super gas barrier of all-polymer multilayer thin films. Macromolecules 44:1450–1459

    Article  CAS  Google Scholar 

  • Yue Y, Zhou C, French A, Xia G, Han G, Wang Q et al (2012) Comparative properties of cellulose nano-crystals from native and mercerized cotton fibers. Cellulose 19:1173–1187

    Article  CAS  Google Scholar 

  • Zhang L, Sun J (2010) Layer-by-layer codeposition of polyelectrolyte complexes and free polyelectrolytes for the fabrication of polymeric coatings. Macromolecules 43:2413–2420

    Article  CAS  Google Scholar 

  • Zhou CJ, Wang QW, Wu QL (2012) UV-initiated crosslinking of electrospun poly(ethylene oxide) nanofibers with pentaerythritol triacrylate: effect of irradiation time and incorporated cellulose nanocrystals. Carbohydr Polym 87:1779–1786

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We wish to thank Prof. Franco Faoro from Department of Plant Production, Università degli Studi di Milano (Milano, Italy), who carried out TEM observations, Dr. Roberto Galbasini and Dr. Giorgio Bottini, from Goglio S. p. A. (VA, Italy), who helped in oxygen and water vapor barrier measurements, and Dr. Christian Furiosi from SAPICI S. p. A (Milan, Italy), who helped in particle size distribution measurement.

Author information

Authors and Affiliations

  1. Packaging Division, Department of Food, Environmental and Nutritional Sciences (DeFENS), Università degli Studi di Milano, Via Celoria, 2, 20133, Milan, Italy

    Fei Li & Luciano Piergiovanni

  2. Dipartimento di Fisica and CNISM, Politecnico di Milano, Piazza Leonardo da Vinci, 32, 20133, Milan, Italy

    Paolo Biagioni

  3. IFN-CNR, L-NESS, Via Anzani 42, 22100, Como, Italy

    Monica Bollani

  4. Packaging Division, GOGLIO S.p.A., Via dell’Industria 7, 21020, Daverio, VA, Italy

    Andrea Maccagnan

Authors
  1. Fei Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Paolo Biagioni
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Monica Bollani
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Andrea Maccagnan
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Luciano Piergiovanni
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Fei Li.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Li, F., Biagioni, P., Bollani, M. et al. Multi-functional coating of cellulose nanocrystals for flexible packaging applications. Cellulose 20, 2491–2504 (2013). https://doi.org/10.1007/s10570-013-0015-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-013-0015-3

Keywords

Search

Navigation