Abstract
High aspect ratio cellulose nanocrystals (CNCs) extracted from tunicate were used to create so-called cryogels from an ice-templating directional freeze-drying process. The structure of the resulting solid foam was investigated at the micro- and nanoscales by scanning electron microscopy and nitrogen adsorption measurements were used to extract the specific surface area. The mechanical properties were probed by compression tests. To highlight the specificities of tunicate CNC-based cryogels, results were compared with the one obtained from two other types of nanocellulose, namely cellulose nanofibrils (CNFs) from wood and CNCs from cotton, which exhibit different dimensions, aspect ratio, flexibility and crystallinity. While CNF- and cotton CNC-based cryogels exhibited a classical morphology characterized by a sheet-like structure, a particular honeycomb organization with individual particles was obtained in the case of tunicate CNC cryogels. The latter cryogels presented a very high specific surface area of about 122 m2 g−1, which is unexpected for foams prepared from a water-based process and much higher than what was obtained for CNF and cotton CNC cryogels (25 and 4 m2 g−1, respectively). High mechanical resistance and stiffness were also obtained with such tunicate CNC cryogels. These results are explained by the high crystallinity, aspect ratio and rigidity of the tunicate CNCs combined with the particular honeycomb architecture of the cryogel.
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Abbreviations
- CNFs:
-
Cellulose nanofibrils
- CNCs:
-
Cellulose nanocrystals
- SEM:
-
Scanning electron microscopy
- TEM:
-
Transmission electron microscopy
- BET:
-
Brunauer, Emmett, Teller
- DLS:
-
Dynamic light scattering
- NMR:
-
Nuclear magnetic resonance
- NLDFT:
-
Nonlocal density functional theory
- AFM:
-
Atomic force microscopy
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Acknowledgments
This work was supported by a grant from Labex ARCANE and CBH-EUR-GS (ANR-17-EURE-0003) and supported by the “Investissement d’avenir” program Glyco@Alps (ANR-15-IDEX-02). The authors acknowledge the Borregaard company for providing CNF materials and thank Jean-Luc Putaux and Christine Lancelon-Pin (CERMAV, Grenoble) for the electron microscopy images and Stéphanie Pradeau (CERMAV, Grenoble) for the measurement of the hemicellulose content in the CNF material. LGP2 is part of the LabEx Tec 21 (Investissements d’Avenir—Grant Agreement No. ANR-11-LABX-0030) and of PolyNat Carnot Institute (Investissements d’Avenir—Grant Agreement No. ANR-16-CARN-0025-01). CD would like to thank Laurent Orgéas (3SR laboratory, Grenoble) for fruitful discussion.
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Darpentigny, C., Molina-Boisseau, S., Nonglaton, G. et al. Ice-templated freeze-dried cryogels from tunicate cellulose nanocrystals with high specific surface area and anisotropic morphological and mechanical properties. Cellulose 27, 233–247 (2020). https://doi.org/10.1007/s10570-019-02772-8
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DOI: https://doi.org/10.1007/s10570-019-02772-8