Water-resistant, transparent hybrid nanopaper by physical cross-linking with chitosan

Biomacromolecules. 2015 Mar 9;16(3):1062-71. doi: 10.1021/acs.biomac.5b00145. Epub 2015 Feb 20.

Abstract

One of the major, but often overlooked, challenges toward high end applications of nanocelluloses is to maintain their high mechanical properties under hydrated or even fully wet conditions. As such, permanent covalent cross-linking or surface hydrophobization are viable approaches, however, the former may hamper processability and the latter may have adverse effect on interfibrillar bonding and resulting material strength. Here we show a concept based on physical cross-linking of cellulose nanofibers (CNF, also denoted as microfibrillated cellulose, MFC, and, nanofibrillated cellulose, NFC) with chitosan for the aqueous preparation of films showing high mechanical strength in the wet state. Also, transparency (∼70-90% in the range 400-800 nm) is achieved by suppressing aggregation and carefully controlling the mixing conditions: Chitosan dissolves in aqueous medium at low pH and under these conditions the CNF/chitosan mixtures form easily processable hydrogels. A simple change in the environmental conditions (i.e., an increase of pH) reduces hydration of chitosan promoting multivalent physical interactions between CNF and chitosan over those with water, resulting effectively in cross-linking. Wet water-soaked films of CNF/chitosan 80/20 w/w show excellent mechanical properties, with an ultimate wet strength of 100 MPa (with corresponding maximum strain of 28%) and a tensile modulus of 4 and 14 GPa at low (0.5%) and large (16%) strains, respectively. More dry films of similar composition display strength of 200 MPa with maximum strain of 8% at 50% air relative humidity. We expect that the proposed, simple concept opens new pathways toward CNF-based material utilization in wet or humid conditions, which has still remained a challenge.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cellulose / chemistry
  • Chitosan / chemistry*
  • Hydrogen-Ion Concentration
  • Hydrophobic and Hydrophilic Interactions
  • Nanofibers / chemistry*
  • Optical Phenomena
  • Paper*
  • Tensile Strength
  • Water / chemistry

Substances

  • Water
  • Cellulose
  • Chitosan