, Volume 23, Issue 1, pp 529–543 | Cite as

Concentration driven cocrystallisation and percolation in all-cellulose nanocomposites

  • Denis Lourdin
  • Jorge Peixinho
  • Joël Bréard
  • Bernard Cathala
  • Eric Leroy
  • Benoît DucheminEmail author
Original Paper


All-cellulose nanocomposites reinforced by cellulose nanocrystals (CNC) were produced using a solvent consisting of 1-butyl-3-methylimidazolium chloride and dimethyl sulfoxide. Microcrystalline cellulose (MCC) was pre-dissolved at high temperature in the solvent. Freeze-dried CNC were then added to the slurry at room temperature, thereby avoiding complete CNC dissolution. Solid all-cellulose composite films were obtained by film casting, solvent exchange and drying. The MCC to CNC ratio was kept constant while the solvent content was incremented. The short-range and long-range cellulose–cellulose interactions in the solid materials were respectively assessed by Fourier-transform infrared spectroscopy and X-ray diffraction. The CNC used in this work contained both cellulose I and cellulose II. The cellulose concentration in the mixture drastically changed the overall crystallinity as well as the cellulose I to cellulose II ratio in the ACC. Cellulose II was formed by recrystallisation of the dissolved fractions. These fractions include the pre-dissolved MCC and the cellulose II portion of the CNC. Cocrystallisation with the cellulose I CNC acting as a template was also evidenced. This phenomenon was controlled by the initial solvent content. The correlation between the hygromechanical properties and the nanostructure features of the ACC was investigated by humidity-controlled dynamic mechanical analysis (RH-DMA). The introduction of the cocrystallisation and percolation concepts provided a thorough explanation for the humidity dependency of the storage modulus.


Cellulose Ionic liquid Crystallization Confinement DMA 



Atomic force microscopy


Transmission electron microscopy


Fourier-transform infrared spectroscopy


Wide-angle X-ray diffraction


Humidity-controlled dynamic mechanical analysis


1-Butyl-3-methylimidazolium chloride


Microcrystalline cellulose


Cellulose nanocrystals


Dimethyl sulfoxide


All-cellulose composites


Regenerated cellulose film


Lateral order index


Total crystallinity index



The authors would like to thank Emilie Perrin (BIA) for her help with the TEM. Financial support from the CNRS was provided through a PEPS grant (BioMIMCellwalL). BD would like to dedicate this article to the memory of the late Dr Roger H. Newman.

Supplementary material

10570_2015_805_MOESM1_ESM.doc (862 kb)
Supplementary material 1 (DOC 891 kb)


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Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  • Denis Lourdin
    • 1
  • Jorge Peixinho
    • 2
  • Joël Bréard
    • 2
  • Bernard Cathala
    • 1
  • Eric Leroy
    • 3
  • Benoît Duchemin
    • 2
    Email author
  1. 1.UR1268 Biopolymères Interactions AssemblagesINRANantesFrance
  2. 2.Laboratoire Ondes et Milieux Complexes, UMR 6294CNRS-Université du HavreLe HavreFrance
  3. 3.CNRS, GEPEA, UMR 6144, CRTTLUNAM UniversitéSt Nazaire CedexFrance

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