Advertisement

Cellulose

, Volume 16, Issue 6, pp 1025–1032 | Cite as

Molecularly thin nanoparticles from cellulose: isolation of sub-microfibrillar structures

  • Qingqing Li
  • Scott RenneckarEmail author
Article

Abstract

We have succeeded in isolating nanostructures from never-dried cellulose wood pulp, in sheet-form that have sub-microfibril dimensions (single to double digit Å thickness with 100’s of nm in length). A recently developed oxidation procedure by Saito and co-workers (Biomacromolecules 2006, 7:1687–1691) combined with extensive ultrasonication was used to liberate nanoscale cellulose fibrils. We show structures, as determined with atomic force microscopy, that compose the well-known cellulose microfibril, which are tenfold thinner than previous reports on nanoscale celluloses. This work provides indirect evidence in support of, and is consistent with, the hypothesis that the intersheet van der Waals bonding of the cellulose fibril is significantly weaker than the intrasheet hydrogen bonding of the cellulose microfibril. The structures are facile to isolate, contain enormous specific surface area with rich chemical functionality providing potential for numerous novel applications.

Keywords

Atomic force microscopy Microfibril Nanocellulose Cellulose nanocrystal Microfibrillated cellulose 

Notes

Acknowledgments

We appreciate the generous financial support of the Institute of Critical Technology and Applied Science, College of Natural Resources, and the Department of Wood Science and Forest Products at Virginia Tech. We also would like to acknowledge Richard K. Johnson for informative discussions around the oxidation process of cellulose fibers.

References

  1. Beck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromolecules 6:1048–1054CrossRefGoogle Scholar
  2. Ding SY, Himmel ME (2006) The maize primary cell wall microfibril: a new model derived from direct visualization. J Agric Food Chem 54:597–606CrossRefGoogle Scholar
  3. Doktycz SJ, Suslick KS (1990) Interparticle collisions driven by ultrasound. Science 247:1067–1069CrossRefGoogle Scholar
  4. Duchesne I, Hult E-L, Molin U, Daniel G, Iversen T, Lennholm H (2001) The influence of hemicellulose on fibril aggregation of kraft pulp fibres as revealed by FE-SEM and CP/MAS 13C-NMR. Cellulose 8:103–111CrossRefGoogle Scholar
  5. Elazzouzi-Hafraoui S, Nishiyama Y, Putaux J-L, Heux L, Dubreuil F, Rochas C (2008) The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose. Biomacromolecules 9:57–65CrossRefGoogle Scholar
  6. Fengel D (1970) Ultrastructural behavior of cell wall polysaccharides. Tappi 53:497–503Google Scholar
  7. Frey-Wyssling A (1954) The fine structure of cellulose microfibrils. Science 119:80–82CrossRefGoogle Scholar
  8. Jakob HF, Fengel D, Tschegg SE, Fratzl P (1995) The elementary cellulose fibril in picea abies: comparison of transmission electron microscopy, small-angle X-ray scattering, and wide-angle X-ray scattering results. Macromolecules 28:8782–8787CrossRefGoogle Scholar
  9. Johnson R, Zink-Sharp A, Renneckar S, Glasser WG (2009) A new bio-based nanocomposite: fibrillated TEMPO-oxidized celluloses in hydroxypropylcellulose matrix. Cellulose 16:227–238CrossRefGoogle Scholar
  10. Klemm D, Heublein B, Fink H-P, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Edit 44:3358–3393CrossRefGoogle Scholar
  11. Lu KL, Lago RM, Chen YK, Green MLH, Harris PJF, Tsang SC (1996) Mechanical damage of carbon nanotubes by ultrasound. Carbon 34:814–816CrossRefGoogle Scholar
  12. Mueller M, Czihak C, Vogl G, Fratzl P, Schober H, Riekel C (1998) Direct observation of microfibril arrangement in a single native cellulose fiber by microbeam small-angle X-ray scattering. Macromolecules 31:3953–3957CrossRefGoogle Scholar
  13. Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose Iβ from synchrotron x-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082CrossRefGoogle Scholar
  14. Nishiyama Y, Kim UJ, Kim DY, Katsumata KS, May RP, Langan P (2003a) Periodic disorder along ramie cellulose microfibrils. Biomacromolecules 4:1013–1017CrossRefGoogle Scholar
  15. Nishiyama Y, Sugiyama J, Chanzy H, Langan P (2003b) Crystal structure and hydrogen bonding system in cellulose Iα from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 125:14300–14306CrossRefGoogle Scholar
  16. Nishiyama Y, Johnson GP, French AD, Forsyth VT, Langan P (2008) Neutron crystallography, molecular dynamics, and quantum mechanics studies of the nature of hydrogen bonding in cellulose Iβ. Biomacromolecules 9:3133–3140CrossRefGoogle Scholar
  17. Paakko M, Ankerfors M, Kosonen H, Nykanen A, Ahola S, Osterberg M, Ruokolainen J, Laine J, Larsson PT, Ikkala O, Lindstrom T (2007) Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels. Biomacromolecules 8:1934–1941CrossRefGoogle Scholar
  18. Patel GM (1951) Optical investigations on oxycelluloses. Makromolekulare Chemie 7:12–45CrossRefGoogle Scholar
  19. Qian XH, Ding SY, Nimlos MR, Johnson DK, Himmel ME (2005) Atomic and electronic structures of molecular crystalline cellulose I beta: a first-principles investigation. Macromolecules 38:10580–10589CrossRefGoogle Scholar
  20. Rao BCS, Buckley DH (1984) Deformation and erosion of FCC metals and alloys under cavitiation attack. Mat Sci Eng 67:55–67CrossRefGoogle Scholar
  21. Saito T, Isogai A (2004) TEMPO-mediated oxidation of native cellulose. The effect of oxidation conditions on chemical and crystal structures of the water-insoluble fractions. Biomacromolecules 5:1983–1989CrossRefGoogle Scholar
  22. Saito T, Shibata I, Isogai A, Suguri N, Sumikawa N (2005) Distribution of carboxylate groups introduced into cotton linters by the TEMPO-mediated oxidation. Carbohydr Polym 61:414–419CrossRefGoogle Scholar
  23. Saito T, Nishiyama Y, Putaux J-L, Vignon M, Isogai A (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 7:1687–1691CrossRefGoogle Scholar
  24. Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8:2485–2491CrossRefGoogle Scholar
  25. Suslick KS (1990) Sonochemistry. Science 247:1439–1445CrossRefGoogle Scholar
  26. VanCleef M, Holt SA, Watson GS, Myhra S (1996) Polystyrene spheres on mica substrates: AFM calibration, tip parameters and scan artefacts. J Microsc (Oxf) 181:2–9CrossRefGoogle Scholar
  27. Wagberg L, Decher G, Norgren M, Lindstrom T, Ankerfors M, Axnas K (2008) The build-up of polyelectrolyte multilayers of microfibrillated cellulose and cationic polyelectrolytes. Langmuir 24:784–795CrossRefGoogle Scholar
  28. Wang Y, Chen XY (2007) Carbon nanotubes: a promising standard for quantitative evaluation of AFM tip apex geometry. Ultramicroscopy 107:293–298CrossRefGoogle Scholar
  29. Wuhrmann K, Heuberger A, Muhlethaler K (1946) Electron-microscopic investigations of cellulose fibers after supersonic treatment. Experientia 2:105–107CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2009

Authors and Affiliations

  1. 1.Department of Wood Science and Forest Products, Institute for Critical Technology and Applied Science Doctoral ScholarVirginia TechBlacksburgUSA
  2. 2.Department of Wood Science and Forest ProductsVirginia TechBlacksburgUSA

Personalised recommendations