, Volume 18, Issue 4, pp 1063–1072 | Cite as

Sorption of dyes on cellulose II: effect of alkali treatment of fibre and dye structure

  • Parikshit Goswami
  • Richard S. Blackburn
  • Jim Taylor
  • Patrick White


Cellulose is a linear 1,4-β-glucan polymer where the units are able to form highly ordered structures, as a result of extensive interaction through intra- and intermolecular hydrogen bonding of the three hydroxyl groups in each cellulose unit. Alkali has a substantial influence on morphological, molecular and supramolecular properties of cellulose II polymer fibres causing changes in crystallinity. Lyocell fibres pre-treated with 0.0, 2.0, and 4.0 mol dm−3 aqueous NaOH solution were dyed with hydrolyzed reactive dyes that had different molecular shapes and sizes. Overall exhaustion (qe), value of K, and −ΔG increased for lyocell samples pre-treated with aqueous NaOH solution in the following order: 2.0 > 4.0 > 0.0 mol dm−3 NaOH. The same trends were observed for colour strength (K/S) values of the dyeings. Pre-treatment of lyocell with 2.0 mol dm−3 NaOH creates the substrate that achieves the most thermodynamically favourable system for sorption of hydrolyzed reactive dyes, as at this concentration crystallinity decreases (with respect to 0.0 mol dm−3 NaOH treated lyocell) to afford higher sorption; however, at higher alkali concentrations the macro-sorbent forms a compacted unit that limits diffusion within the sorbent interior. Molecular size of the sorbate dye has a significant effect on the sorption process: for the largest dye structure the sorption isotherm is most closely correlated to a Langmuir isotherm; as the size of the dye decreases correlation to a Langmuir isotherm is observed, but with good correlation to the Freundlich isotherm; as the size of the dye is decreased further sorption is more typical of a Freundlich isotherm.


Freundlich isotherm Langmuir isotherm Adsorption Polysaccharides Lyocell Sodium hydroxide Adsorption Hydrolyzed reactive dye 


  1. Albrecht W, Reintjes M, Wulfhorst B (1997) Lyocell fibres. Chem Fibers Int 47:298–304Google Scholar
  2. Alila S, Boufi S, Belgacem MN, Beneventi D (2005) Adsorption of a cationic surfactant onto cellulosic fibres—I. Surface charge effects. Langmuir 21:8106–8113CrossRefGoogle Scholar
  3. Blackburn RS, Harvey A, Kettle LL, Manian AP, Payne JD, Russell SJ (2007) Sorption of Chlorhexidine on cellulose: mechanism of binding and molecular recognition. J Phys Chem B 111:8775–8784CrossRefGoogle Scholar
  4. Carrillo F, Lis MJ, Valldeperas J (2002) Sorption isotherms and behaviour of direct dyes on lyocell fibres. Dye Pigment 53:129–136CrossRefGoogle Scholar
  5. Colom X, Carrillo F (2002) Crystallinity changes in lyocell and viscose-type fibres by caustic treatment. Eur Polym J 38:2225–2230CrossRefGoogle Scholar
  6. Freundlich H (1906) Concerning adsorption in solutions. Z Phys Chem 57:385–470Google Scholar
  7. Gindl W, Martinschitz KJ, Boesecke P, Keckes J (2006) Changes in the molecular orientation and tensile properties of uniaxially drawn cellulose films. Biomacromolecules 7:3146–3150CrossRefGoogle Scholar
  8. Goswami P, Blackburn RS, Westland S, Taylor J, White P (2007) Dyeing behaviour of lyocell fabric: effect of fibrillation. Color Technol 123:387–393CrossRefGoogle Scholar
  9. Goswami P, Blackburn RS, El-Dessouky HM, Taylor J, White P (2009a) Effect of sodium hydroxide pre-treatment on the optical and structural properties of lyocell. Eur Polym J 45:455–465CrossRefGoogle Scholar
  10. Goswami P, Blackburn RS, Taylor J, White P (2009b) Dyeing behaviour of lyocell fabric: effect of NaOH pre-treatment. Cellulose 16:481–489CrossRefGoogle Scholar
  11. Ibbett RN, Hsieh YL (2001) Effect of fiber swelling on the structure of lyocell fabrics. Text Res J 71:164–173CrossRefGoogle Scholar
  12. Ibbett RN, Kaenthong S, Phillips DAS, Wilding MA (2006a) Characterisation of the porosity of regenerated cellulosic fibres using classical dye adsorption techniques. Lenzinger Berichte 85:77–86Google Scholar
  13. Ibbett RN, Phillips DAS, Kaenthong S (2006b) Evaluation of a dye isotherm method for characterisation of the wet-state structure and properties of lyocell fibre. Dye Pigment 71:168–177CrossRefGoogle Scholar
  14. Inglesby MK, Zeronian SH (2002) Direct dyes as molecular sensors to characterize cellulose substrates. Cellulose 9:19–29CrossRefGoogle Scholar
  15. Klemm D, Heublein B, Fink H-P, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:3358–3393CrossRefGoogle Scholar
  16. Kolpak FJ, Blackwell J (1976) Determination of the structure of cellulose II. Macromolecules 9:273–278CrossRefGoogle Scholar
  17. Kono H, Numata Y (2004) Two-dimensional spin-exchange solid-state NMR study of the crystal structure of cellulose II. Polymer 45:4541–4547CrossRefGoogle Scholar
  18. Kreze T, Malej S (2003) Structural characteristics of new and conventional regenerated cellulosic fibres. Text Res J 73:675–684CrossRefGoogle Scholar
  19. Langan P, Nishiyama Y, Chanzy H (1999) A revised structure and hydrogen-bonding system in cellulose II from a neutron fibre diffraction analysis. J Am Chem Soc 121:9940–9946CrossRefGoogle Scholar
  20. Langmuir I (1916) The constitution and fundamental properties of solids and liquids. Part I. solids. J Am Chem Soc 38:2221–2295CrossRefGoogle Scholar
  21. Langmuir I (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc 40:1361–1403CrossRefGoogle Scholar
  22. Luo M, Zhang XL, Chen SL (2003). Enhancing the wash fastness of dyeings by a sol–gel process. Part 1. Direct dyes on cotton. Color Technol 119:297–300 CrossRefGoogle Scholar
  23. McDonald R (1980) Industrial pass-fail colour matching. 3. Development of a pass-fail formula for use with instrumental measurement of colour difference. J Soc Dye Colour 96:486–497CrossRefGoogle Scholar
  24. Okano T, Sarko A (1984) Mercerization of cellulose. I. X-ray diffraction evidence for intermediate structures. J Appl Polym Sci 29:4175–4182CrossRefGoogle Scholar
  25. Okano T, Sarko A (1985) Mercerization of cellulose. II. Alkali-cellulose intermediates and a possible mercerization mechanism. J Appl Polym Sci 30:325–332CrossRefGoogle Scholar
  26. Öztürk HB, Potthast A, Rosenau T, Abu-Rous M, MacNaughtan B, Schuster CK, Mitchell JR, Bechtold T (2009) Changes in the intra- and inter-fibrillar structure of lyocell (TENCEL A®) fibres caused by NaOH treatment. Cellulose 16:37–52CrossRefGoogle Scholar
  27. Široký J, Blackburn RS, Bechtold T, Taylor J, White P (2010) Attenuated total reflectance fourier-transform Infrared spectroscopy analysis of crystallinity changes in lyocell following continuous treatment with sodium hydroxide. Cellulose 17:103–115CrossRefGoogle Scholar
  28. Široký J, Blackburn RS, Bechtold T, Taylor J, White P (2011) Alkali treatment of cellulose II fibres and effect on dye sorption. Carbohydr Polym 84:299–307CrossRefGoogle Scholar
  29. Wang Q, Hauser PJ (2009) New characterization of layer-by-layer self-assembly deposition of polyelectrolytes on cotton fabric. Cellulose 16:1123–1131CrossRefGoogle Scholar
  30. White P, Hayhurst M, Taylor J, Slater A (2005). Lyocell fibres. In: Blackburn RS (ed) Biodegradable and sustainable fibres. Woodhead Publishing Limited, CambridgeGoogle Scholar
  31. Zhou LM, Yeung KW, Yuen CWM, Zhou X (2003) Effect of mercerisation and crosslinking on the dyeing properties of ramie fabric. Color Technol 119:170–176CrossRefGoogle Scholar
  32. Zhu Y, Ren X, Wu C (2004) Influence of alkali treatment on the structure of newcell fibres. J Appl Polym Sci 93:1731–1735CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  • Parikshit Goswami
    • 1
  • Richard S. Blackburn
    • 1
  • Jim Taylor
    • 2
  • Patrick White
    • 2
  1. 1.Green Chemistry Group, Centre for Technical TextilesUniversity of LeedsLeedsUK
  2. 2.Lenzing FibersLenzingAustria

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