Abstract
Oriented films were prepared from aqueous suspensions of cellulose nanocrystal (CNC; microfibril fragment of sulfuric acid-hydrolyzed cotton) by a shearing method. Rotating glass vials each containing a 3–4 wt% CNC/water suspension under evaporation resulted in formation of translucent films of CNC per se. Structural characterization of the dry films was carried out by use of X-ray diffractometry and optical and scanning electron microscopy. The orientation pattern of CNCs in the films was much affected by pH condition of the starting suspensions; that is, the longitudinal axes of CNCs aligned preferentially perpendicular to the shear direction (SD) in the acidic condition of pH = 2.0, while an ordinary orientation of CNCs aligning parallel to SD was observed in the neutral condition of pH = 6.7 (adjusted with NaOH addition to the acidic suspension, however). To interpret the two distinct orientation patterns, first, it was inspected whether a mesomorphic ordered phase arrived or not in the two sheared and dried suspensions, different from each other in the counterions of surface-sulfated CNCs. As to the orientation development from the suspension of pH = 2, it was particularly assumed that the arising nematic planar domains would have been rolled up into a transversely extended body with the director perpendicular to SD. For the two film preparations, the orientation parameter of the longitudinal axis of CNC was quantified by WAXD intensity measurements, and the data were compared with those for other CNC-oriented materials such as CNC/polymer composites synthesized by immobilizing CNC suspensions via magnetic field application.
Similar content being viewed by others
References
Bartram E, Goldsmith HL, Mason SG (1975) Particle motions in non-Newtonian media III. further observations in elasticoviscous fluids. Rheol Acta 14:776–782
Chen B, Tatsumi D, Matsumoto T (2003) Fiber orientation and flow properties of pulp fiber suspensions under shear flow conditions. Sen’i Gakkaishi 59:471–478
Dong XM, Gray DG (1997) Effects of counterions on ordered phase formation in suspensions of charged rodlike cellulose crystallites. Langmuir 13:2404–2409
Dong XM, Kimura T, Revol J-F, Gray DG (1996) Effects of ionic strength on the isotropic-chiral nematic phase transition of suspensions of cellulose crystallites. Langmuir 12:2076–2082
Dong XM, Revol J-F, Gray DG (1998) Effect of microcrystallite preparation conditions on the formation of colloid crystals of cellulose. Cellulose 5:19–32
Dufresne A (2010) Processing of polymer nanocomposites reinforced with polysaccharide nanocrystals. Molecules 15:4111–4128
Ebeling T, Paillet R, Borsali R, Diat O, Dufresne A, Cavaillé J-Y, Chanzy H (1999) Shear-induced orientation phenomena in suspensions of cellulose microcrystals, revealed by small angle X-ray scattering. Langmuir 15:6123–6126
Eichhorn SJ (2011) Cellulose nanowhiskers: promising materials for advanced applications. Soft Matter 7:303–315
Gindle W, Keckes J (2007) Drawing of self-reinforced cellulose films. J Appl Polym Sci 103:2703–2708
Gray DG (1994) Chiral nematic ordering of polysaccharides. Carbohydr Polym 25:277–284
Gunes DZ, Scirocco R, Mewis J, Vermant J (2008) Flow-induced orientation of non-spherical particles: effect of aspect ratio and medium rheology. J Non-Newtonian Fluid Mech 155:39–50
Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110:3479–3500
Iso Y, Koch DL, Cohen C (1996) Orientation in simple shear flow of semi-dilute fiber suspensions 1. weaky elastic fluids. J Non-Newtonian Fluid Mech 62:115–134
Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray DG, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed 50:5438–5466
Kvien I, Oksman K (2007) Orientation of cellulose nanowhiskers in polyvinyl alcohol. Appl Phys A Mater Sci Process 87:641–643
Majoinen J, Kontturi E, Ikkala O, Gray DG (2012) SEM imaging of chiral nematic films cast from cellulose nanocrystal suspensions. Cellulose 19:1599–1605
Marchessault RH, Morehead FF, Walter NM (1959) Liquid crystal systems from fibrillar polysaccharides. Nature 184:632–633
Miao C, Hamad WY (2013) Cellulose reinforced polymer composites and nanocomposites: a critical review. Cellulose 20:2221–2262
Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994
Navard P (1987) Optical properties of a shear-deformed thermotropic cellulose derivative. J Polym Sci, Part B: Polym Phys 25:1089–1098
Nishio Y, Yamane T, Takahashi T (1985) Morphological studies of liquid-crystalline cellulose derivatives. II. Hydroxypropyl cellulose films prepared from liquid-crystalline aqueous solutions. J Polym Sci Polym Phys Ed 23:1053–1064
Nishiyama Y, Kuga S, Wada M, Okano T (1997) Cellulose microcrystal film of high uniaxial orientation. Macromolecules 30:6395–6397
Orts WJ, Godbout L, Marchessault RH, Revol J-F (1998) Enhanced ordering of liquid crystalline suspensions of cellulose microfibrils: a small angle neutron scattering study. Macromolecules 31:5717–5725
Pullawan T, Wilkinson AN, Eichhorn SJ (2012) Influence of magnetic field alignment of cellulose whiskers on the mechanics of all-cellulose nanocomposites. Biomacromolecules 13:2528–2536
Revol J-F, Bradford H, Giasson J, Marchessault RH, Gray DG (1992) Helicoidal self-ordering of cellulose microfibrils in aqueous suspension. Int J Biol Macromol 14:170–172
Sugiyama J, Vuong R, Chanzy H (1991) Electron diffraction study on the two crystalline phases occurring in native cellulose from an algal cell wall. Macromolecules 24:4168–4175
Tatsumi M, Teramoto Y, Nishio Y (2012) Polymer composites reinforced by locking-in a liquid-crystalline assembly of cellulose nanocrystallites. Biomacromolecules 13:1584–1591
Tatsumi M, Kimura F, Kimura T, Teramoto Y, Nishio Y (2014) Anisotropic polymer composites synthesized by immobilizing cellulose nanocrystal suspensions specifically oriented under magnetic fields. Biomacromolecules 15:4579–4589
Uddin AJ, Araki J, Gotoh Y (2011) Toward “strong” green nanocomposites: polyvinyl alcohol reinforced with extremely oriented cellulose whiskers. Biomacromolecules 12:617–624
Ureña-Benavides EE, Brown PJ, Kitchens CL (2010) Effect of jet stretch and particle load on cellulose nanocrystal-alginate nanocomposite fibers. Langmuir 26:14263–14270
Acknowledgments
This work was financially supported by a Grant-in-Aid for Scientific Research (A) (No. 26252025 to Y.N.) from the Japan Society for the Promotion of Science.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no conflict of interest.
Rights and permissions
About this article
Cite this article
Tatsumi, M., Teramoto, Y. & Nishio, Y. Different orientation patterns of cellulose nanocrystal films prepared from aqueous suspensions by shearing under evaporation. Cellulose 22, 2983–2992 (2015). https://doi.org/10.1007/s10570-015-0722-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-015-0722-z