Skip to main content
SpringerLink
Log in

The behaviour of cationic NanoFibrillar Cellulose in aqueous media

  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

Explore related subjects

Discover the latest articles, news and stories from top researchers in related subjects.

References

  • Ahola S, Salmi J, Johansson LS, Laine J, Österberg M (2008a) Model films from native cellulose nanofibrils. Preparation, swelling, and surface interactions. Biomacromolecules 9:1273–1282

    Article  CAS  Google Scholar 

  • Ahola S, Österberg M, Laine J (2008b) Cellulose nanofibrils-adsorption with poly(amideamine) epichlorohydrin studied by QCM-D and application as a paper strength additive. Cellulose 15:303–314

    Article  CAS  Google Scholar 

  • Aulin C, Ahola S, Josefsson P, Nishino T, Hirose Y, Österberg M, Wågberg L (2009) Nanoscale cellulose films with different crystallinities and mesostructures; their surface properties and interaction with water. Langmuir 25:7675–7685

    Article  CAS  Google Scholar 

  • Aulin C, Johansson E, Wågberg L, Lindström T (2010) Self-organized films from Cellulose I nanofibrils using the layer-by-layer technique. Biomacromolecules 11:872–882

    Article  CAS  Google Scholar 

  • Baker AA, Helbert W, Sugiyama J, Miles MJ (1997) High-resolution atomic force microscopy of native valonia cellulose I microcrystals. J Struct Biol 119:129–138

    Article  CAS  Google Scholar 

  • Bardage S, Donaldson L, Tokoh T, Daniel G (2004) Ultrastructure of the cell wall of unbeaten Norway spruce pulp fibre surfaces. Nord Pulp Pap Res J 19:448–452

    Article  CAS  Google Scholar 

  • Beamson G, Briggs D (1992) High Resolution XPS of organic polymers. The Scienta ESCA300 Database. Wiley, Chichester

    Google Scholar 

  • Decher G, Schlenoff JB (2003) Multilayer Thin Films: Sequential assembly of nanocomposite Materials. Wiley-VCH, Weinheim

    Google Scholar 

  • Ding S-Y, Himmel ME (2006) The maize primary cell wall microfibril: a new model derived from direct visualization. J Argic Food Chem 54:597–606

    Article  CAS  Google Scholar 

  • Dufresne A, Dupeyre D, Paillet M (2003) Lignocellulosic flour-reinforced poly(hydroxybutyrate-co-valerate) composites. J Appl Polym Sci 87:1302–1315

    Article  CAS  Google Scholar 

  • Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Capadona JR, Rowan SJ, Weder C, Thielemans W, Roman M, Renneckar S, Gindl W, Veigel S, Keckes J, Yano H, Abe K, Nogi M, Nakagaito AN, Mangalam A, Simonsen J, Benight AS, Bismarck A, Berglund LA, Peijs T (2010) Review: current international research into cellulose nanofibres and nanocomposites. J Mater Sci 45:1–33

    Article  CAS  Google Scholar 

  • Eronen P, Österberg M, Jääskeläinen A-S (2009) Effect of alkaline treatment on cellulose supramolecular structure studied with combined confocal Raman spectroscopy and atomic force microscopy. Cellulose 16:167–178

    Article  CAS  Google Scholar 

  • Fahlen J, Salmen L (2003) Cross-sectional structure of the secondary wall of wood fibers as affected by processing. J Mater Sci 38:119–126

    Article  CAS  Google Scholar 

  • Fält S, Wågberg L, Vesterlind EL (2003) Swelling of model films of cellulose having different charge densities and comparison tot he swelling behavior of corresponding fibers. Langmuir 19:7895–7903

    Article  Google Scholar 

  • Flory JP (1953) Principles of Polymer Chemistry. Cornell University Press, Ithaca

    Google Scholar 

  • Gilbert P, Moore LE (2005) Cationic antiseptics: diversity of action under a common epithet. J Appl Microbiol 99:703–715

    Article  CAS  Google Scholar 

  • Gross AS, Chu J-W (2010) On the molecular origins of biomass recalcitrance: the interaction network and solvation structures of cellulose microfibrils. J Phys Chem B 114:13333–13341

    Article  CAS  Google Scholar 

  • Hult EL, Larsson PT, Iversen T (2001) Cellulose fibril aggregation—an inherent property of kraft pulps. Polymer 42:3309–3314

    Article  CAS  Google Scholar 

  • Iwamato S, Abe K, Yano H (2008) The Effect of Hemicelluloses on wood pulp nanofibrillation and nanofiber network characteristics. Biomacromolecules 9:1022–1026

    Article  Google Scholar 

  • Iwamoto S, Kai WH, Isogai A, Iwata T (2009) Elastic modulus of single cellulose microfibrils from tunicate measured by atomic force microscopy. Biomacromolecules 10:2571–2576

    Article  CAS  Google Scholar 

  • Jakob HF, Fengel D, Tschegg SE, Fratzl P (1995) The elementary cellulose fibril in picea abies: comparison of transmission electron microscopy, small-angle S-ray scattering, and wide-angle X-ray scattering results. Macromolecules 28:8782–8787

    Article  CAS  Google Scholar 

  • Johannsmann D, Mathauer K, Wegner G, Knoll W (1992) Viscoelastic properties of thin films probed with quartz-crystal resonator. Phys Rev B 46:7808–7815

    Google Scholar 

  • Johansson L-S, Campbell JM (2004) Reproducible XPS on biopolymers: cellulose studies. Surf Interface Anal 36:1018–1022

    Article  CAS  Google Scholar 

  • Johansson L-S, Campbell JM, Kaljonen K, Kleen M, Buchert J (2004) On surface distributions in natural cellulosic fibres. Surf Interface Anal 36:706–710

    Article  CAS  Google Scholar 

  • Johnson RK, Zink-Sharp A, Renneckar SH, Glasser WG (2009) A new bio-based nanocomposite: fibrillated TEMPO-oxidized celluloses in hydroxypropylcellulose matrix. Cellulose 16:227–238

    Article  CAS  Google Scholar 

  • Katz K, Beatson RP, Scallan AM (1984) The determination of strong and weak acidic groups in sulphite pulps. Svensk Papperstidning 87(6):R48–R53

    CAS  Google Scholar 

  • Kondo T (1997) The relationship between intramolecular hydrogen bonds and certain physical properties of regioselectively substituted cellulose derivatives. J Polym Sci Part B Polym Phys 35:717–723

    Article  CAS  Google Scholar 

  • Kontturi E, Tammelin T, Österberg M (2006) Cellulose-model films and the fundamental approach. Chem Soc Rev 35:1287–1304

    Article  CAS  Google Scholar 

  • Li Q, Renneckar S (2009) Molecularly thin nanoparticles from cellulose: isolation of sub-microfibrillar structures. Cellulose 16:1025–1032

    Article  Google Scholar 

  • Meshitsuka G, Isogai A (1996) Chemical structures of cellulose hemicellulose and lignin. In: Hon DN-S (ed) Chemical modification of lignocellulosic materials. Marcel decker, New York, pp 11–33

    Google Scholar 

  • Mwaikambo LY, Ansell MP (2001) The determination of porosity and cellulose content of plant fibers by density methods. J Mater Sci Lett 20:2095–2096

    Article  CAS  Google Scholar 

  • Naderi A, Claesson PM (2006) Adsorption properties of polyelectrolyte-surfactant complexes on hydrophobic surfaces studied by QCM-D. Langmuir 22:7639–7645

    Article  CAS  Google Scholar 

  • Pääkkö M, Ankerfors M, Kosonen H, Nykänen A, Ahola S, Österberg M, Ruokolainen J, Laine J, Larsson PT, Ikkala O, Lindström T (2007) Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels. Biomacromolecules 8:1934–1941

    Article  Google Scholar 

  • Phillips DL, Xing J, Liu H, Chong CK, Corke H (1999) Raman spectroscopic determination of the degree of cationic modification in waxy maize starches. Anal Letters 32:3049–3058

    Article  CAS  Google Scholar 

  • Pigorsch E (2009) Spectroscopic characterization of cationic quarternary ammonium starches. Starch 61:129–138

    Article  CAS  Google Scholar 

  • Saito T, Nishiyama Y, Putaux J-L, Vignon M (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 7:1687–1691

    Article  CAS  Google Scholar 

  • Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8:2485–2491

    Article  CAS  Google Scholar 

  • Sakurada I, Nukushina Y, Ito T (1962) Experimental determination of the elastic modulus of crystalline regions in oriented polymers. J Polym Sci 57:651–660

    Article  CAS  Google Scholar 

  • Salmi J, Nypelö T, Österberg M, Laine J (2009) Layer Structure formed by silica nanoparticles and cellulose nanofibril with cationic polyacrylamide (C-PAM) on cellulose surface and their influence on interactions. Bioresources 4:602–625

    CAS  Google Scholar 

  • Sauerbrey G (1959) The use of quartz oscillators for weighing thin layers and for microweighing. Z Phys 155:206–222

    Article  CAS  Google Scholar 

  • Siró I, Plackett D (2010) Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose 17:459–495

    Article  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Taipale T, Österberg M, Nykänen A, Ruokolainen J, Laine J (2010) Effect of microfibrillated cellulose and fines on the drainage of kraft pulp suspension and paper strength. Cellulose 17:1005–1020

    Article  CAS  Google Scholar 

  • Tammelin T, Saarinen T, Österberg M, Laine J (2006) Preparation of Langmuir/Blodgett-cellulose surfaces by using horizontal dipping procedure. Application for polyelectrolyte adsorption studies performed with QCM-D. Cellulose 13:519–535

    Article  CAS  Google Scholar 

  • Vietor RJ, Newman RH, Ha MA, Apperley DC, Jarvis MC (2002) Conformational features of crystal-surface cellulose from higher plants. Plant J 30:721–731

    Article  CAS  Google Scholar 

  • Virtanen T, Maunu SL, Tamminen T, Hortling B, Liitiä T (2008) Changes in fiber ultrastructure during various kraft pulping conditions evaluated by 13C CPMAS NMR spectroscopy. Carbohydr Polym 73:156–163

    Article  CAS  Google Scholar 

  • Wågberg L, Winter L, Ödberg L, Lindström T (1987) On the charge stoichiometry upon adsorption of a cationic polyelectrolyte on cellulosic materials. Colloids Surf 27:163–173

    Google Scholar 

  • Wågberg L, Decher G, Norgren M, Lindström T, Ankerfors M, Axnäs K (2008) The build-up of polyelectrolyte multilayers of microfibrillated cellulose and cationic polyelectrolytes. Langmuir 24:784–795

    Article  Google Scholar 

  • Wählby C, Erlandsson F, Nyberg K, Lindblad J, Zetterberg A, Bengtsin E (2001) Proceedings of 12th scandinavian conference on image analysis, Bergen, Norway

  • Wang Y, Chen HY (2007) Carbon nanotubes: a promising standard for quantitative evaluation of AFM tip apex geometry. Ultramicroscopy 107:293–298

    Article  CAS  Google Scholar 

  • Wang M, Olszewska A, Walther A, Malho J-M, Schacher FH, Ruokalainen J, Ankerors M, Laine J, Berglund LA, Österberg M, Ikkala O (2011) Colloidal ionic self-assembly between anionic native cellulose nanofibrils and cationic lock copolymer micelles into biomimetic nano-composites. Biomacromolecules 12:2074–2081

    Google Scholar 

  • Wiley JH, Atalla RH (1987) Band assignments in the Raman spectra of celluloses. Carbohydrates Res 160:113–129

    Article  CAS  Google Scholar 

  • Yano H, Sugiyama J, Nakagaito AN, Nogi M, Matsuura T, Kikita M, Handa K (2005) Optically transparent composites reinforced with networks of bacterial nanofibers. Adv Mater 17:153–155

    Article  CAS  Google Scholar 

  • Zimmermann T, Pöhler E, Geiger T (2004) Cellulose fibrils for polymer reinforcement. Adv Eng Mater 6:754–761

    Article  Google Scholar 

Download references

Acknowledgments

This work has been performed as a part of “Design Cell” project in the Wood Wisdom.net. National Technology Agency of Finland, UPM Kymmene Corporation, Metso Oyj and Kemira Oyj is acknowledged for financial support. AO wishes to express her gratitude to Dr. Eero Kontturi for his help and inspiring scientific discussions. The experimental assistance of Marja Kärkkäinen is gratefully acknowledged. Joanna Hornatowska, Innventia, is acknowledged for here assistance in determining the size distribution in AFM-images.

Author information

Authors and Affiliations

  1. Department of Forest Products Technology, School of Chemical Technology, Aalto University, P.O. Box 16300, 00076, Aalto, Finland

    Anna Olszewska, Paula Eronen, Leena-Sisko Johansson, Janne Laine & Monika Österberg

  2. Department of Applied Physics, School of Science, Aalto University, P.O. Box 15100, Puumiehenkuja 2, 00076, Espoo, Finland

    Jani-Markus Malho & Janne Ruokolainen

  3. INNVENTIA, AB Box 5604, Drottning Kristinas väg 61, 114 86, Stockholm, Sweden

    Mikael Ankerfors & Tom Lindström

Authors
  1. Anna Olszewska
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Paula Eronen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Leena-Sisko Johansson
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jani-Markus Malho
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Mikael Ankerfors
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Tom Lindström
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Janne Ruokolainen
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Janne Laine
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Monika Österberg
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Anna Olszewska or Monika Österberg.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Olszewska, A., Eronen, P., Johansson, LS. et al. The behaviour of cationic NanoFibrillar Cellulose in aqueous media. Cellulose 18, 1213–1226 (2011). https://doi.org/10.1007/s10570-011-9577-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-011-9577-0

Keywords

Search

Navigation