, Volume 25, Issue 7, pp 4057–4066 | Cite as

Highly transparent 100% cellulose nanofibril films with extremely high oxygen barriers in high relative humidity

  • Jianyu Xia
  • Zhe Zhang
  • Wei Liu
  • Vincent C. F. Li
  • Yunfeng Cao
  • Wei Zhang
  • Yulin Deng
Original Paper


Highly transparent films with excellent gas barriers are very attractive materials for electronic devices. However, gas barrier properties of conventional cellulose nanofibril films tend to degrade under humid conditions. It is a great challenge to obtain nanocellulose films that simultaneously have very low gas permeability, high transparency, and high moisture and water resistance. In this study, free-standing, highly transparent films with excellent oxygen barrier properties were prepared from cellulose nanofibrils (CNF), followed by post-thermal treatment. Also, reducing agent was introduced to reduce discoloration during heating. CNF films showed high transparency (85–90% at 600 nm). SEM images indicated the loss of porous structure after thermal treatment, resulting in higher gas barriers and lower water retention values. Film showed extremely low oxygen permeability value of 0.007 ml μm kPa−1 m−2 day−1 at 23 °C and 50% relative humidity (RH) after treatment at 145 °C. Even at 80% RH, the oxygen permeability is only 0.584 ml μm kPa−1 m−2 day−1, which is 100 times lower than most plastic films such as poly(ethylene terephthalate) and poly(vinyl chloride).


Cellulose nanofibril Thermal treatment Oxygen barrier Transparency 



Jianyu Xia would like to thank the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), the Doctorate Fellowship Foundation of Nanjing Forestry University and National Natural Science Foundation of China (No. 31670597) for the financial support. And the work was supported by Dr. Deng’s group from RBI at Georgia Tech.


  1. Aulin C, Gällstedt M, Lindström T (2010) Oxygen and oil barrier properties of icrofibrillated cellulose films and coatings. Cellulose 17:559–574. CrossRefGoogle Scholar
  2. 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. CrossRefPubMedGoogle Scholar
  3. Bayer IS et al (2011) Water-repellent cellulose fiber networks with multifunctional properties. ACS Appl Mater Interfaces 3:4024–4031. CrossRefPubMedGoogle Scholar
  4. Belbekhouche S et al (2011) Water sorption behavior and gas barrier properties of cellulose whiskers and microfibrils films. Carbohydr Polym 83:1740–1748. CrossRefGoogle Scholar
  5. Benhamou K, Kaddami H, Magnin A, Dufresne A, Ahmad A (2015) Bio-based polyurethane reinforced with cellulose nanofibers: a comprehensive investigation on the effect of interface. Carbohydr Polym 122:202–211. CrossRefPubMedGoogle Scholar
  6. Bhuiyan MTR, Hirai N, Sobue N (2000) Changes of crystallinity in wood cellulose by heat treatment under dried and moist conditions. J Wood Sci 46:431–436. CrossRefGoogle Scholar
  7. Brancato A, Walsh FL, Sabo R, Banerjee S (2007) Effect of recycling on the properties of paper surfaces. Ind Eng Chem Res 46:9103–9106. CrossRefGoogle Scholar
  8. Charton C, Schiller N, Fahland M, Holländer A, Wedel A, Noller K (2006) Development of high barrier films on flexible polymer substrates. Thin Solid Films 502:99–103. CrossRefGoogle Scholar
  9. Chen Y, Wang Y, Wan J, Ma Y (2010) Crystal and pore structure of wheat straw cellulose fiber during recycling. Cellulose 17:329–338. CrossRefGoogle Scholar
  10. Chen Y-M, Wan J-Q, Huang M-Z, Ma Y-W, Wang Y, Lv H-L, Yang J (2011) Influence of drying temperature and duration on fiber properties of unbleached wheat straw pulp Carbohydrate polymers 85:759–764. Google Scholar
  11. Diniz JF, Gil M, Castro J (2004) Hornification—its origin and interpretation in wood pulps. Wood Sci Technol 37:489–494. CrossRefGoogle Scholar
  12. Fang Z et al (2014) Novel nanostructured paper with ultrahigh transparency and ultrahigh haze for solar cells. Nano Lett 14:765–773. CrossRefPubMedGoogle Scholar
  13. French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. CrossRefGoogle Scholar
  14. Hu L et al (2013) Transparent and conductive paper from nanocellulose fibers. Energy Environ Sci 6:513–518. CrossRefGoogle Scholar
  15. Hult E-L, Larsson P, Iversen T (2001) Cellulose fibril aggregation—an inherent property of kraft pulps. Polymer 42:3309–3314. CrossRefGoogle Scholar
  16. Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85. CrossRefPubMedGoogle Scholar
  17. Jonoobi M, Harun J, Mathew AP, Hussein MZB, Oksman K (2010) Preparation of cellulose nanofibers with hydrophobic surface characteristics. Cellulose 17:299–307. CrossRefGoogle Scholar
  18. 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. CrossRefGoogle Scholar
  19. Lange J, Wyser Y (2003) Recent innovations in barrier technologies for plastic packaging—a review. Pack Technol Sci 16:149–158. CrossRefGoogle Scholar
  20. Le D, Kongparakul S, Samart C, Phanthong P, Karnjanakom S, Abudula A, Guan G (2016) Preparing hydrophobic nanocellulose-silica film by a facile one-pot method. Carbohydr Polym 153:266–274. CrossRefPubMedGoogle Scholar
  21. Lu T, Li Q, Chen W, Yu H (2014) Composite aerogels based on dialdehyde nanocellulose and collagen for potential applications as wound dressing and tissue engineering scaffold. Compos Sci Technol 94:132–138. CrossRefGoogle Scholar
  22. Missoum K, Martoïa F, Belgacem MN, Bras J (2013) Effect of chemically modified nanofibrillated cellulose addition on the properties of fiber-based materials. Ind Crops Prod 48:98–105. CrossRefGoogle Scholar
  23. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994. CrossRefPubMedGoogle Scholar
  24. Mulyadi A, Deng Y (2016) Surface modification of cellulose nanofibrils by maleated styrene block copolymer and their composite reinforcement application. Cellulose 23:519–528. CrossRefGoogle Scholar
  25. Nishiyama Y (2009) Structure and properties of the cellulose microfibril. J Wood Sci 55:241–249. CrossRefGoogle Scholar
  26. Noack M, Schneider M, Dittmar A, Georgi G, Caro J (2009) The change of the unit cell dimension of different zeolite types by heating and its influence on supported membrane layers. Microporous Mesoporous Mater 117:10–21. CrossRefGoogle Scholar
  27. Okahisa Y, Yoshida A, Miyaguchi S, Yano H (2009) Optically transparent wood–cellulose nanocomposite as a base substrate for flexible organic light-emitting diode displays. Compos Sci Technol 69:1958–1961. CrossRefGoogle Scholar
  28. 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. CrossRefPubMedGoogle Scholar
  29. Östlund Å, Köhnke T, Nordstierna L, Nydén M (2010) NMR cryoporometry to study the fiber wall structure and the effect of drying. Cellulose 17:321–328. CrossRefGoogle Scholar
  30. Park S, Venditti RA, Jameel H, Pawlak JJ (2006) Changes in pore size distribution during the drying of cellulose fibers as measured by differential scanning calorimetry. Carbohydr Polym 66:97–103. CrossRefGoogle Scholar
  31. 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. CrossRefGoogle Scholar
  32. Saito T, Nishiyama Y, Putaux J-L, Vignon M, Isogai A (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 7:1687–1691. CrossRefPubMedGoogle Scholar
  33. Sehaqui H, Zimmermann T, Tingaut P (2014) Hydrophobic cellulose nanopaper through a mild esterification procedure. Cellulose 21:367–382. CrossRefGoogle Scholar
  34. Sharma PR, Varma AJ (2014) Thermal stability of cellulose and their nanoparticles: effect of incremental increases in carboxyl and aldehyde groups. Carbohydr Polym 114:339–343. CrossRefPubMedGoogle Scholar
  35. Sharma S, Zhang X, Nair SS, Ragauskas A, Zhu J, Deng Y (2014) Thermally enhanced high performance cellulose nano fibril barrier membranes. RSC Adv 4:45136–45142. CrossRefGoogle Scholar
  36. Shimizu M, Saito T, Fukuzumi H, Isogai A (2014) Hydrophobic, ductile, and transparent nanocellulose films with quaternary alkylammonium carboxylates on nanofibril surfaces. Biomacromolecules 15:4320–4325. CrossRefPubMedGoogle Scholar
  37. Shimizu M, Saito T, Isogai A (2016) Water-resistant and high oxygen-barrier nanocellulose films with interfibrillar cross-linkages formed through multivalent metal ions. J Membr Sci 500:1–7. CrossRefGoogle Scholar
  38. 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. CrossRefPubMedGoogle Scholar
  39. Sirviö JA, Kolehmainen A, Visanko M, Liimatainen H, Niinimäki J, Hormi OE (2014) Strong, self-standing oxygen barrier films from nanocelluloses modified with regioselective oxidative treatments. ACS Appl Mater Interfaces 6:14384–14390. CrossRefPubMedGoogle Scholar
  40. Song Z, Xiao H, Zhao Y (2014) Hydrophobic-modified nano-cellulose fiber/PLA biodegradable composites for lowering water vapor transmission rate (WVTR) of paper. Carbohydr Polym 111:442–448. CrossRefPubMedGoogle Scholar
  41. Stanssens D, Van den Abbeele H, Vonck L, Schoukens G, Deconinck M, Samyn P (2011) Creating water-repellent and super-hydrophobic cellulose substrates by deposition of organic nanoparticles. Mater Lett 65:1781–1784. CrossRefGoogle Scholar
  42. Takaichi S, Saito T, Tanaka R, Isogai A (2014) Improvement of nanodispersibility of oven-dried TEMPO-oxidized celluloses in water. Cellulose 21:4093–4103. CrossRefGoogle Scholar
  43. Urbina L et al (2016) Biodegradable composites with improved barrier properties and transparency from the impregnation of PLA to bacterial cellulose membranes. J Appl Polym Sci 133. CrossRefGoogle Scholar
  44. Wu J, Zheng Y, Yang Z, Lin Q, Qiao K, Chen X, Peng Y (2013) Influence of dialdehyde bacterial cellulose with the nonlinear elasticity and topology structure of ECM on cell adhesion and proliferation. RSC Adv 4:3998–4009. CrossRefGoogle Scholar
  45. Yagyu H, Saito T, Isogai A, Koga H, Nogi M (2015) Chemical modification of cellulose nanofibers for the production of highly thermal resistant and optically transparent nanopaper for paper devices. ACS Appl Mater Interfaces 7:22012–22017. CrossRefPubMedGoogle Scholar
  46. Yang Q, Saito T, Isogai A (2012) Facile fabrication of transparent cellulose films with high water repellency and gas barrier properties. Cellulose 19:1913–1921. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  • Jianyu Xia
    • 1
    • 2
  • Zhe Zhang
    • 2
  • Wei Liu
    • 2
  • Vincent C. F. Li
    • 2
  • Yunfeng Cao
    • 1
  • Wei Zhang
    • 3
  • Yulin Deng
    • 2
  1. 1.College of Light Industry and Food ScienceNanjing Forestry UniversityNanjingChina
  2. 2.School of Chemical and Biomolecular Engineering and RBI at Georgia TechGeorgia Institute of TechnologyAtlantaUSA
  3. 3.State Key Laboratory of Polymer Materials Engineering, Polymer Research InstituteSichuan UniversityChengduChina

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