, Volume 16, Issue 5, pp 825–832 | Cite as

Analysis of CMC attachment onto cellulosic fibers by infrared spectroscopy

  • E. Gilli
  • A. E. Horvath
  • A. T. Horvath
  • U. Hirn
  • R. Schennach


Infrared spectroscopy has been used to measure the amount of carboxymethyl cellulose (CMC) attached to cellulosic fibers. CMC was attached to an unbleached kraft pulp in aqueous conditions. Isotropic handsheets were then prepared and ATR spectroscopy was used to measure the intensity of the carboxyl vibration, which correlates to the amount of attached CMC that was determined using a wet chemical approach. The ATR method is rather time consuming as several measurement points on the sample have to be averaged, although it is still much faster than the wet chemical approach. Infrared reflection absorption spectroscopy (IRRAS) using polarized light was further used to measure the amount of attached CMC. In this method the intensity of an electromagnetic wave confined to the thin layer is used to correlate the spectroscopy to the amount of CMC on the fiber surface in the paper sample. The measurement time is shorter than with the ATR method. The proposed IRRAS method could be employed as a fast and reliable way to quantify adsorption of chemicals on pulp fibers.


FTIR IRRAS CMC ATR Paper fibers 



Funding by the Christian Doppler Society is greatly appreciated. E. Gilli and R. Schennach are indebted to P. Knoll for helpful discussions.


  1. Barzyk D, Page DH, Ragauskas A (1997a) Acidic group topochemistry and fibre-to-fibre specific bond strength. J Pulp Pap Sci 23(2):J59–J61Google Scholar
  2. Barzyk D, Page DH, Ragauskas A (1997b) Carboxylic acids groups and fibre bonding. In: The fundamentals in papermaking materials: the transaction of the 11th fundamental research symposium, vol 2. Cambridge, UK, pp 893–907Google Scholar
  3. Berreman DW (1969) Infrared absorption at longitudinal optic frequency in cubic crystal films. Phys Rev 130:2193–2198. doi: 10.1103/PhysRev.130.2193 CrossRefGoogle Scholar
  4. Borstel G, Falge HJ (1977) Surface phonon—polaritons at semi infinite crystals. Phys Status Solidi B 83(11):11–45Google Scholar
  5. Duker E, Lindström T (2008) On the mechanisms behind the ability of CMC to enhance paper strength. Nordic Pulp Pap Res J 23(1):57–64. doi: 10.3183/NPPRJ-2008-23-01-p057-064 CrossRefGoogle Scholar
  6. Gilli E (2008) IR spectroscopic investigations on the chemical surface properties of cellulose fibers. Diploma thesis, Graz University of Technology, GrazGoogle Scholar
  7. Harbecke B, Heinz B, Grosse P (1985) Optical properties of thin films and the Berreman effect. Appl Phys A 38:263–267. doi: 10.1007/BF00616061 CrossRefGoogle Scholar
  8. Hoffman H, Mayer U, Krischanitz A (1995) Structure of alkylsiloxane monolayers on silicon surfaces investigated by external reaction infrared spectroscopy. Langmuir 11:1304–1312. doi: 10.1021/la00004a043 CrossRefGoogle Scholar
  9. Hopfield JJ (1965) Polariton absorption lines. Phys Rev Lett 15(1):22–25. doi: 10.1103/PhysRevLett.15.22 CrossRefGoogle Scholar
  10. Horvath AE, Lindström T (2007) Indirect polyelectrolyte titration of cellulosic fibers—surface and bulk charges of cellulosic fibers. Nordic Pulp Pap Res J 22(1):87–92. doi: 10.3183/NPPRJ-2007-22-01-p087-092 CrossRefGoogle Scholar
  11. 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(2):824–830. doi: 10.1021/la052217i CrossRefGoogle Scholar
  12. Katz S, Beatson RP, Scallan AM (1984) The determination of strong and weak acidic groups in sulfite pulps. Svensk Papperstidning 87(6):48–53Google Scholar
  13. Laine J, Lindström T, Glad-Nordmark G, Risinger G (2000) Studies on topochemical modification of cellulosic fibres. Part 1. Chemical conditions for the attachment of carboxymethyl cellulose onto fibres. Nordic Pulp Pap Res J 15(5):520–526. doi: 10.3183/NPPRJ-2000-15-05-p520-526 CrossRefGoogle Scholar
  14. Laine J, Lindström T, Bremberg C, Glad-Nordmark G (2003) Studies on topochemical modification of cellulosic fibres. Part 5. Comparison of the effects of surface and bulk chemical modification and beating of pulps on paper properties. Nordic Pulp Pap Res J 18(3):326–333Google Scholar
  15. Lindström T (1980) Influence of chemical factors on fiber swelling and paper strength. Papier 34(12):561–568Google Scholar
  16. Lindström T (1989) Some fundamental chemical aspects on paper forming. In: Fundamentals of papermaking: transaction of the 9th fundamental research symposium, vol 1. Cambridge, UK, pp 311–412Google Scholar
  17. Lindström T, Wagberg L, Larssson T (2005) On the nature of joint strength in paper—a review of dry and wet strength resins used in paper manufacturing. In: Proceedings of the 13th fundamental research symposium, vol 1. Cambridge, FRC, pp 457–562Google Scholar
  18. Mielczarski JA, Mielczarsky E (1999) Infrared external reection spectroscopy of adsorbed monolayers in a region of strong absorption of substrate. J Phys Chem B 103:5852–5859. doi: 10.1021/jp990529m CrossRefGoogle Scholar
  19. Mielczarski JA, Mielczarsky E (2005) Monitoring mineral surface phenomena by infrared reaction spectroscopy. Physicochem Probl Miner Process 39:33–46Google Scholar
  20. Terayama H (1952) Method of colloid titration (a new titration between polymer ions). J Polymer Sci 8(2):243–253. doi: 10.1002/pol.1952.120080209 CrossRefGoogle Scholar
  21. Tolstoy VP, Chernyshova IV, Skryshevsky VA (2003) Handbook of infrared spectroscopy of ultrathin films. Wiley, HobokenCrossRefGoogle Scholar
  22. Trasferetti BC, Davanzo CU, Da Cruz NC, De Moraes MAB (2000) Observation of the Berreman effect in infrared reflection-absorption spectra of amorphous titanium oxide thin films deposited on aluminum. Appl Spectrosc 54(5):687–691. doi: 10.1366/0003702001949933 CrossRefGoogle Scholar
  23. Wågberg L, Ödberg L, Glad-Nordmark G (1989) Charge determination of porous substrates by polyelectrolyte adsorption. Nordic Pulp Pap Res J 4(2):71–76. doi: 10.3183/NPPRJ-1989-04-02-p071-076 CrossRefGoogle Scholar
  24. Winter L, Wågberg L, Ödberg L, Lindström T (1986) Polyelectrolytes adsorbed on the surface on cellulosic materials. J Colloid Interface Sci 111(2):537–543. doi: 10.1016/0021-9797(86)90057-3 CrossRefGoogle Scholar
  25. Yamamoto K, Ishida H (1994) Optical theory applied to infrared spectroscopy. Vib Spectrosc 8:1–36. doi: 10.1016/0924-2031(94)00022-9 CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2009

Authors and Affiliations

  • E. Gilli
    • 1
    • 2
  • A. E. Horvath
    • 2
    • 3
  • A. T. Horvath
    • 3
  • U. Hirn
    • 2
    • 4
  • R. Schennach
    • 1
    • 2
  1. 1.Institute of Solid State PhysicsGraz University of TechnologyGrazAustria
  2. 2.CD-Laboratory for Surface Chemical and Physical Fundamentals of Paper StrengthGraz University of TechnologyGrazAustria
  3. 3.Mondi Frantschach GmbHFrantschach, Sankt GertraudAustria
  4. 4.Institute of Pulp and Paper TechnologyGraz University of TechnologyGrazAustria

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