Abstract
The higher-order structure of natural cellulose fibres changes in the presence of water. In order to investigate the effect of molecular level fibre structure, melting behaviour of water restrained by nano- and microcellulose fibre was measured by differential scanning calorimetry. Fibre size was measured by scanning electron microscopy and atomic force microscopy. It was found that the melting peak of water restrained by microcellulose fibre started at 250–260 K in a W c (=mass of water/mass of dry sample) range from 0.5 to 1.2, whereas that of nanocellulose fibre was 230–237 K. Furthermore, peak temperature of melting of water restrained by nanocellulose was observed at around 270 K, in contrast, that of water restrained by microcellulose fibre was observed at ca. 275 K. Bound water content was calculated from melting enthalpy. Both non-freezing and freezing bound water of nanocellulose fibre was far larger than that of microcellulose. The above results suggest that a large amount of freezing bound water is restrained in nanocellulose fibres. It is thought that a larger number of isolated hydroxyl groups exist on the fibre surface.
Similar content being viewed by others
References
Siro I, Plackett D. Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose. 2010;17:459–94.
Qua EH, Hornsby PR, Sharma HSS, Lyons G. Preparation and characterisation of cellulose nanofibres. J Mater Sci. 2011;46:6029–45.
Taniguchi T, Okamura K. New films produced from microfibrillated natural fibres. Polym Int. 1998;47:291–4.
Iwamoto S, Nakagaito AN, Yano H, Nogi M. Optically transparent composites reinforced with plant fiber-based nanofibers. Appl Phys. 2005;A81:1109–12.
Nakagaito AN, Yano H. The effect of morphological changes from pulp fiber towards non-scale fibrillated cellulose on the mechanical properties of high-strength plant fiber based composite. Appl Phys. 2004;A78:547–50.
Nakagaito AN, Iwamoto S, Yano H. Bacterial cellulose: the ultimate nano-scalar cellulose morphology for the production of high-strength composites. Appl Phys. 2005;A80:93–7.
Nakagaito AN, Yano H. Novel high-strength biocomposites based on microfibrillated cellulose having nano-order-unit web-like network structure. Appl Phys. 2005;A80:155–9.
Yano H, Nakahara S. Bio-composites produced from plant microfiber bundles with a nano meter unit web-like network. J Mat Sci. 2004;39:1635–938.
Nogi M, Ifuku S, Abe K, Handa K, Nakagaito AN, Yano H. Fiber-content dependency of the optical transparency and thermal expansion of bacterial nanofiber reinforced composites. Appl Phys Lett. 2006;88:133124.
Seydibeyooğle MO, Oksman K. Novel nanocomposites based on polyurethane and micro fibrilled cellulose. Compos Sci Technol. 2008;68:908–14.
Maeda H, Nakajima M, Hagiwara T, Sawaguchi T, Yano S. Bacterial cellulose/silica hybrid fabricated by mimicking biocomposites. J Mat Sci. 2006;41:5646–56.
Yano S, Maeda H, Nakajima M, Hagiwara T, Sawaguchi T. Preparation and mechanical properties of bacterial cellulose nanocomposites loaded with silica nanoparticles. Cellulose. 2008;15:111–20.
Hatakeyama H, Hatakeyama T. Interaction between water and hydrophilic polymers. Thermochim Acta. 1998;308:3–22.
Hatakeyama T, Hatakeyama H. Thermal properties of green polymers and biocomposites. Dordrecht: Kluwer Academic Publishers; 2004.
Hatakeyama T, Tanaka M, Hatakeyama H. Studies on bound water restrained by poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC): comparison of the polysaccharides-water systems. Acta Biomaterilia. 2010;6:2077–82.
Hatakeyama T, Tanaka M, Hatakeyama H. Thermal properties of freezing bound water restrained by polysaccharides. J Biomater Sci. 2010;21:1865–75.
Hatakeyama T, Tanaka M, Kishi A, Hatakeyama H. Comparison of measurement techniques for identification of bound water restrained by polymers. Thermochim Acta. 2012;532:159–63.
Onishi T, Hatakeyama H, Hatakeyama T. DSC and AFM studies of chemically cross-linked sodium cellulose sulfate hydrogels. In: Hu TQ, editor. Characterization of lingocellulosic materials. Cambridge: Blackwell; 2008. p. 329–39.
Aulin C, Ahola S, Josefsson P, Nishino T, Hirose Y, Osterberg M, Wagberg L. Nanoscale cellulose films with different crystallinities and mesostructures; their surface properties and interaction with water. Langmuir. 2009;25:7675–85.
Eronen P, Laine J, Ruokolainen J, Osterberg M. Comparison of multilayer formation between different cellulose nanofibrils and cationic polymers. J Colloid Interface Sci. 2012;373:84–93.
Eyholzer Ch, Bordeanu N, Lopez-Suevos F, Rentsch D, Zimmermann T, Oksman K. Preparation and characterization of water-redispersible nanofibrillated cellulose in powder forms. Cellulose. 2010;17:19–30.
Hatakeyama T, Hatakeyama H. Thermal properties of water around the cross-linking networks in cellulose pseudo hydrogels. In: Kennedy JF, Phillips GO, Williams PA, editors. Cellulosics: chemical, biochemical and material aspects. Chichester: Ellis Horwood; 1993. p. 225–30.
Cellulose Society of Japan. Cellulose handbook. Tokyo: Asakura; 2000. p. 81–102.
Angell CA, Shuppert J, Tucker JC. Anomalous properties of supercooled water. Heat capacity, expansivity, and proton magnetic resonance chemical shift from 0 to −38o. J Phys Chem. 1973;77:3092–7.
Hatakeyama T, Nakamura K, Hatakeyama H. Vaporization of bound water associated with cellulose fibres. Thermochim Acta. 2000;352–353:233–9.
Acknowledgements
The authors extend their sincere thanks to Professor Shigeo Hirose (Fukui University of Technology) for providing us with NCF samples and to Professor Clive S. Langham, Nihon University, for his helpful comments.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Hatakeyama, T., Inui, Y., Iijima, M. et al. Bound water restrained by nanocellulose fibres. J Therm Anal Calorim 113, 1019–1025 (2013). https://doi.org/10.1007/s10973-012-2823-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-012-2823-3