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Concentration driven cocrystallisation and percolation in all-cellulose nanocomposites

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Abstract

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.

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Abbreviations

AFM:

Atomic force microscopy

TEM:

Transmission electron microscopy

FTIR:

Fourier-transform infrared spectroscopy

WAXD:

Wide-angle X-ray diffraction

RH-DMA:

Humidity-controlled dynamic mechanical analysis

BmimCl:

1-Butyl-3-methylimidazolium chloride

MCC:

Microcrystalline cellulose

CNC:

Cellulose nanocrystals

DMSO:

Dimethyl sulfoxide

ACC:

All-cellulose composites

RCF:

Regenerated cellulose film

LOI:

Lateral order index

TCI:

Total crystallinity index

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Acknowledgments

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.

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Authors and Affiliations

  1. UR1268 Biopolymères Interactions Assemblages, INRA, 44300, Nantes, France

    Denis Lourdin & Bernard Cathala

  2. Laboratoire Ondes et Milieux Complexes, UMR 6294, CNRS-Université du Havre, 53 rue Prony, BP540, 76058, Le Havre, France

    Jorge Peixinho, Joël Bréard & Benoît Duchemin

  3. CNRS, GEPEA, UMR 6144, CRTT, LUNAM Université, 37, Boulevard de l’Université, 44606, St Nazaire Cedex, France

    Eric Leroy

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Lourdin, D., Peixinho, J., Bréard, J. et al. Concentration driven cocrystallisation and percolation in all-cellulose nanocomposites. Cellulose 23, 529–543 (2016). https://doi.org/10.1007/s10570-015-0805-x

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