The behaviour of cationic NanoFibrillar Cellulose in aqueous media

This paper deals, with cationically modified NanoFibrillar Cellulose (cat NFC), obtained by reacting a dissolving pulp with 2,3-epoxypropyl trimethylammonium chloride (EPTMAC). The cat NFC was thoroughly characterized in terms of morphology and physical properties. The dimensions of individual cellulose nanofibrils were determined by atomic force microscopy (AFM) imaging in water and in air. Fibrils as thin as 0.8–1.2 nm were observed in water. The fibril diameter changed upon drying and the average size was further quantified by image analysis. The experiments showed the importance of characterizing nanocellulosic materials in situ before drying. The fibril size in air was confirmed by cryogenic transmission electron microscopy (cryo-TEM), and it was found to be 2.6–3.0 nm. Smooth ultrathin films of cationic NFC were prepared by spincoating on silica substrates. The effect of electrolyte concentration and pH on swelling of the cationic NFC film was studied using a quartz crystal microbalance with dissipation. The results showed that at pH = 8 the cat NFC film was insensitive to electrolyte changes while at pH = 4.5, the water content of the film decreased with increasing ionic strength. The electrophoretic mobility measurements showed a cationic zeta potential for the cat NFC that decreased at increasing pH, verifying the swelling behaviour.

[1]  Akira Isogai,et al.  Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. , 2007, Biomacromolecules.

[2]  E. Pigorsch.  Spectroscopic Characterisation of Cationic Quaternary Ammonium Starches , 2009 .

[3]  Ichiro Sakurada,et al.  Experimental determination of the elastic modulus of crystalline regions in oriented polymers , 1962 .

[4]  Akira Isogai,et al.  Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. , 2006, Biomacromolecules.

[5]  C. K. Chong,et al.  Raman Spectroscopic Determination of the Degree of Cationic Modification in Waxy Maize Starches , 1999 .

[6]  R. Newman,et al.  Conformational features of crystal-surface cellulose from higher plants. , 2002, The Plant journal : for cell and molecular biology.

[7]  M. Ansell,et al.  The determination of porosity and cellulose content of plant fibers by density methods , 2001 .

[8]  T. Lindström,et al.  On the charge stoichiometry upon adsorption of a cationic polyelectrolyte on cellulosic materials , 1987 .

[9]  Michael E Himmel,et al.  The maize primary cell wall microfibril: a new model derived from direct visualization. , 2006, Journal of agricultural and food chemistry.

[10]  Hiroyuki Yano,et al.  Optically Transparent Composites Reinforced with Networks of Bacterial Nanofibers , 2005 .

[11]  R. Atalla,et al.  Band assignments in the Raman spectra of celluloses , 1987 .

[12]  Akira Isogai,et al.  Elastic modulus of single cellulose microfibrils from tunicate measured by atomic force microscopy. , 2009, Biomacromolecules.

[13]  J. Sugiyama,et al.  Electron diffraction study on the two crystalline phases occurring in native cellulose from an algal cell wall , 1991 .

[14]  Kentaro Abe,et al.  The effect of hemicelluloses on wood pulp nanofibrillation and nanofiber network characteristics. , 2008, Biomacromolecules.

[15]  J. Buchert,et al.  On surface distributions in natural cellulosic fibres , 2004 .

[16]  J. Chu,et al.  On the molecular origins of biomass recalcitrance: the interaction network and solvation structures of cellulose microfibrils. , 2010, The journal of physical chemistry. B.

[17]  Tiina Nypelö,et al.  Layer structures formed by silica nanoparticles and cellulose nanofibrils with cationic polyacrylamide (C-PAM) on cellulose surface and their influence on interactions , 2009, BioResources.

[18]  D. Briggs,et al.  High Resolution XPS of Organic Polymers: The Scienta ESCA300 Database , 1992 .

[19]  Tetsuo Kondo,et al.  The relationship between intramolecular hydrogen bonds and certain physical properties of regioselectively substituted cellulose derivatives , 1997 .

[20]  Janne Laine,et al.  Effect of microfibrillated cellulose and fines on the drainage of kraft pulp suspension and paper strength , 2010 .

[21]  Magnus Norgren,et al.  The build-up of polyelectrolyte multilayers of microfibrillated cellulose and cationic polyelectrolytes. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[22]  G. Daniel,et al.  Ultrastructure of the cell wall of unbeaten Norway spruce pulp fibre surfaces , 2004 .

[23]  David Plackett,et al.  Microfibrillated cellulose and new nanocomposite materials: a review , 2010 .

[24]  Peter Josefsson,et al.  Nanoscale cellulose films with different crystallinities and mesostructures--their surface properties and interaction with water. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[25]  Scott Renneckar,et al.  Molecularly thin nanoparticles from cellulose: isolation of sub-microfibrillar structures , 2009 .

[26]  Tommi Virtanen,et al.  Changes in fiber ultrastructure during various kraft pulping conditions evaluated by 13C CPMAS NMR spectroscopy , 2008 .

[27]  P. Gilbert,et al.  Cationic antiseptics: diversity of action under a common epithet , 2005, Journal of applied microbiology.

[28]  Leena‐Sisko Johansson,et al.  Model films from native cellulose nanofibrils. Preparation, swelling, and surface interactions. , 2008, Biomacromolecules.

[29]  F. Schacher,et al.  Colloidal ionic assembly between anionic native cellulose nanofibrils and cationic block copolymer micelles into biomimetic nanocomposites. , 2011, Biomacromolecules.

[30]  D. Briggs,et al.  High resolution XPS of organic polymers , 1992 .

[31]  D. Hon.  Chemical modification of lignocellulosic materials , 1996 .

[32]  Johannsmann,et al.  Viscoelastic properties of thin films probed with a quartz-crystal resonator. , 1992, Physical review. B, Condensed matter.

[33]  P. T. Larsson,et al.  Cellulose fibril aggregation — an inherent property of kraft pulps , 2001 .

[34]  Richard K. Johnson,et al.  A new bio-based nanocomposite: fibrillated TEMPO-oxidized celluloses in hydroxypropylcellulose matrix , 2009 .

[35]  M. Österberg,et al.  Effect of alkaline treatment on cellulose supramolecular structure studied with combined confocal Raman spectroscopy and atomic force microscopy , 2009 .

[36]  A. Dufresne,et al.  Lignocellulosic flour‐reinforced poly(hydroxybutyrate‐co‐valerate) composites , 2003 .

[37]  E. Johansson,et al.  Self-organized films from cellulose I Nanofibrils using the layer-by-layer technique. , 2010, Biomacromolecules.

[38]  P. Claesson,et al.  Adsorption properties of polyelectrolyte-surfactant complexes on hydrophobic surfaces studied by QCM-D. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[39]  L. Wågberg,et al.  Swelling of model films of cellulose having different charge densities and comparison to the swelling behavior of corresponding fibers , 2003 .

[40]  Helbert,et al.  High-Resolution Atomic Force Microscopy of Native Valonia Cellulose I Microcrystals , 1997, Journal of structural biology.

[41]  Thomas Geiger,et al.  Cellulose Fibrils for Polymer Reinforcement , 2004 .

[42]  M. Österberg,et al.  Preparation of Langmuir/Blodgett-cellulose Surfaces by Using Horizontal Dipping Procedure. Application for Polyelectrolyte Adsorption Studies Performed with QCM-D , 2006 .

[43]  Kentaro Abe,et al.  Review: current international research into cellulose nanofibres and nanocomposites , 2010, Journal of Materials Science.

[44]  Eero Kontturi,et al.  Cellulose--model films and the fundamental approach. , 2006, Chemical Society reviews.

[45]  Carbon nanotubes: a promising standard for quantitative evaluation of AFM tip apex geometry. , 2007 .

[46]  Gero Decher,et al.  Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials , 2003 .

[47]  Peter Fratzl,et al.  The elementary cellulose fibril in Picea abies : comparison of transmission electron microscopy, small-angle X-ray scattering, and wide-angle X-ray scattering results , 1995 .

[48]  O. Ikkala,et al.  Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels. , 2007, Biomacromolecules.

[49]  P. Flory.  Principles of polymer chemistry , 1953 .

[50]  Leena-Sisko Johansson,et al.  Reproducible XPS on biopolymers: cellulose studies , 2004 .

[51]  G. Sauerbrey.  Verwendung von Schwingquarzen zur Wägung dünner Schichten und zur Mikrowägung , 1959 .

[52]  G. Sauerbrey,et al.  Use of quartz vibration for weighing thin films on a microbalance , 1959 .

[53]  L. Salmén,et al.  Cross-sectional structure of the secondary wall of wood fibers as affected by processing , 2003 .

[54]  M. Österberg,et al.  Cellulose nanofibrils—adsorption with poly(amideamine) epichlorohydrin studied by QCM-D and application as a paper strength additive , 2008 .