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Cellulose

, Volume 20, Issue 6, pp 2887–2895 | Cite as

Titrimetric methods for the determination of surface and total charge of functionalized nanofibrillated/microfibrillated cellulose (NFC/MFC)

  • Karoliina JunkaEmail author
  • Ilari Filpponen
  • Tom Lindström
  • Janne Laine
Original Paper

Abstract

Total and surface charge of three different carboxymethylated nanofibrillated/microfibrillated cellulose (NFC/MFC) samples were investigated by using titrimetric methods (conductometric and polyelectrolyte (PE) titrations). Conductometric titration was found to be suitable method for the NFC total charge measurements when the back titration with HCl was applied. Surface charge measurements of NFC/MFC were conducted by using both indirect and direct PE titrations. The direct PE titration was found to be a more suitable method for the surface charge determination of NFC/MFC whereas the indirect PE titration produced too high surface charge values. This is presumably due to kinetically locked polyelectrolyte conformations on the NFC/MFC surfaces or entrapment of residual polymer after adsorption onto the NFC/MFC gel network. Finally, NFC was propargyl-functionalized and the changes in surface and total charge were successfully monitored and compared to those of propargyl-functionalized pulp. A good correlation between the titrimetric methods and elemental analysis was observed.

Keywords

Nanofibrillated cellulose Charge density Surface charge Total charge Propargyl-NFC 

Notes

Acknowledgments

This work was funded by Naseva2 project. Graduate School for Biomass Refining (BIOREGS) and Refining Lignocellulosics to Advanced Polymers and Fibers (PolyRefNorth) network are thanked for personal financial support (KJ). Ms. Gunborg Glad-Nordmark, Ms. Åsa Blademo, Ms. Ritva Kivelä, Ms. Anu Anttila, Ms. Marja Kärkkäinen and Ms. Johanna Mareta are thanked for laboratory assistance. KJ acknowledges fruitful discussions with Ali Naderi and Jonas Sundström (Innventia AB).

References

  1. Chakraborty A, Sain M, Kortschot M (2005) Cellulose microfibrils: a novel method of preparation using high shear refining and cryocrushing. Holzforschung 59:102–107CrossRefGoogle Scholar
  2. Filpponen I, Argyropoulos DS (2010) Regular linking of cellulose nanocrystals via click chemistry: synthesis and formation of cellulose nanoplatelet gels. Biomacromolecules 11:1060–1066CrossRefGoogle Scholar
  3. Filpponen I, Kontturi E, Nummelin S, Rosilo H, Kolehmainen E, Ikkala O, Laine J (2012) Generic method for modular surface modification of cellulosic materials in aqueous medium by sequential “click” reaction and adsorption. Biomacromolecules 13:736–742CrossRefGoogle Scholar
  4. Herrick FW, Casebier RL, Hamilton JK, Sandberg KR (1983) Microfibrillated cellulose: morphology and accessibility. J Appl Polym Sci Appl Polym Symp 37:797–813Google Scholar
  5. Horvath AE, Lindström T, Laine J (2006) On the indirect polyelectrolyte titration of cellulosic fibers. Conditions for charge stoichiometry and comparison with ESCA. Langmuir 22:824–830CrossRefGoogle Scholar
  6. Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85CrossRefGoogle Scholar
  7. Johansson L, Tammelin T, Campbell JM, Setälä H, Österberg M (2011) Experimental evidence on medium driven cellulose surface adaptation demonstrated using nanofibrillated cellulose. Soft Matter 7:10917–10924CrossRefGoogle Scholar
  8. Junka K, Filpponen I, Johansson L, Kontturi E, Rojas OJ, Laine J (2012) A method for the heterogeneous modification of nanofibrillar cellulose in aqueous media. Carbohydr Polym. doi: 10.1016/j.carbpol.2012.11.063 Google Scholar
  9. Katz S, Beatson RP, Scallan AM (1984) The determination of strong and weak acidic groups in sulfite pulps. Sven Papperstidn 87:R48–R53Google Scholar
  10. Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Edit 50:5438–5466CrossRefGoogle Scholar
  11. Lavoine N, Desloges I, Dufresne A, Bras J (2012) Microfibrillated cellulose—its barrier properties and applications in cellulosic materials: a review. Carbohydr Polym 90:735–764CrossRefGoogle Scholar
  12. Littunen K, Hippi U, Johansson L, Österberg M, Tammelin T, Laine J, Seppälä J (2011) Free radical graft copolymerization of nanofibrillated cellulose with acrylic monomers. Carbohydr Polym 84:1039–1047CrossRefGoogle Scholar
  13. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994CrossRefGoogle Scholar
  14. 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 homogenisation for nanoscale cellulose fibrils and strong gels. Biomacromolecules 8:1934–1941CrossRefGoogle Scholar
  15. Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibres prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8:2485–2491CrossRefGoogle Scholar
  16. Solala I, Volperts A, Andersone A, Dizhbite T, Mironova-Ulmane N, Vehniäinen A, Pere J, Vuorinen T (2011) Mechanoradical formation and its effects on birch kraft pulp during the preparation of nanofibrillated cellulose with Masuko refining. Holzforschung 66:477–483Google Scholar
  17. Swerin A, Ödberg L, Lindström T (1990) Deswelling of hardwood kraft pulp fibres by cationic polymers: the effect of wet pressing and sheet properties. Nord Pulp Pap Res J 5:188–196CrossRefGoogle Scholar
  18. Taniguchi T (1996) Microfibrillation of natural fibrous materials. J Soc Mater Sci Jpn 45:472–473Google Scholar
  19. Turbak AF, Snyder FW, Sandberg KR (1983) Microfibrillated cellulose, a new cellulose product: properties, uses and commercial potential. J Appl Polym Sci Appl Polym Symp 37:815–827Google Scholar
  20. Wågberg L, Winter L, Ödberg L, Lindström T (1987) On the charge stoichiometry upon adsorption of a cationic polyelectrolyte on cellulosic materials. Colloids Surf 27:163–173Google Scholar
  21. Walecka JA (1956) An investigation of low degree of substitution carboxymethylcelluloses. Tappi J 39:458–463Google Scholar
  22. Winter L, Wågberg L, Ödberg L, Lindström T (1986) Polyelectrolytes adsorbed on the surface of cellulosic materials. J Colloid Interface Sci 111:537–543CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2013

Authors and Affiliations

  • Karoliina Junka
    • 1
    Email author
  • Ilari Filpponen
    • 1
  • Tom Lindström
    • 2
  • Janne Laine
    • 1
  1. 1.Department of Forest Products TechnologyAalto University School of Chemical TechnologyAaltoFinland
  2. 2.Innventia ABStockholmSweden

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