Polyelectrolyte Complexes for Tailoring of Wood Fibre Surfaces

  • Caroline Ankerfors
  • Lars Wågberg
Part of the Advances in Polymer Science book series (POLYMER, volume 256)


The use of polyelectrolyte complexes (PECs) provides new opportunities for surface engineering of solid particles in aqueous environments to functionalize the solids either for use in interactive products or to tailor their adhesive interactions in the dry and/or wet state. This chapter describes the use of PECs in paper-making applications where the PECs are used for tailoring the surfaces of wood-based fibres. Initially a detailed description of the adsorption process is given, in more general terms, and in this respect both in situ formed and pre-formed complexes are considered. When using in situ formed complexes, which were intentionally formed by the addition of oppositely charged polymers, it was established that the order of addition of the two polyelectrolytes was important, and by adding the polycation first a more extensive fibre flocculation was found. PECs can also form in situ by the interaction between polyelectrolytes added and polyelectrolytes already present in the fibre suspension originating from the wood material, e.g. lignosulphonates or hemicelluloses. In this respect the complexation can be detrimental for process efficiency and/or product quality depending on the charge balance between the components, and when using the PECs for fibre engineering it is not recommended to rely on in situ PEC formation. Instead the PECs should be pre-formed before addition to the fibres. The use of pre-formed PECs in the paper-making process is described as three sub-processes: PEC formation, adsorption onto surfaces, and the effect on the adhesion between surfaces. The addition of PECs, and adsorption to the fibres, prior to formation of the paper network structure has shown to result in a significant increase in joint strength between the fibres and to an increased strength of the paper made from the fibres. The increased joint strength between the fibres is due to both an increased molecular contact area between the fibres and an increased molecular adhesion. The increased paper strength is also a result of an increased number of fibre/fibre contacts/unit volume of the paper network.


Fibre Surface Kraft Pulp Pulp Fibre Paper Sheet Fibre Suspension 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


  1. 1.
    Davison RW (1972) Weak link in paper dry strength. Tappi 55:567–573Google Scholar
  2. 2.
    Page DH (1969) Theory for the tensile strength of paper. Tappi 52:674–681Google Scholar
  3. 3.
    Lindström T, Wågberg L, Larsson T (2005) On the nature of joint strength in paper - A review of dry and wet strength resins used in paper manufacturing. In: I’Anson SJ (ed) Advances in paper science and technology: transactions of the13th fundamental research symposium, Cambridge, UK, Sept 2005. Pulp and Paper Fundamental Research Society, Bury, UK, pp 457-562Google Scholar
  4. 4.
    Torgnysdotter A, Wågberg L (2006) Tailoring of fibre/fibre joints in order to avoid the negative impacts of drying on paper properties. Nord Pulp Pap Res J 21:411–418CrossRefGoogle Scholar
  5. 5.
    Decher G, Hong JD, Schmitt J (1992) Buildup of ultrathin multilayer films by a self-assembly process: III. Consecutively alternating adsorption of anionic and cationic polyelectrolytes on charged surfaces. Thin Solid Films 210/211:831–835CrossRefGoogle Scholar
  6. 6.
    Wågberg L, Forsberg S, Johansson A et al (2002) Engineering of fibre surface properties by application of the polyelectrolyte multilayer concept. Part I: modification of paper strength. J Pulp Pap Sci 28:222–227Google Scholar
  7. 7.
    Page DH (1985) The mechanism of strength development of dried pulps by beating. Svensk Papperstid 88:R30–R35Google Scholar
  8. 8.
    Ankerfors C (2012) Polyelectrolyte complexes: preparation, characterization, and use for control of wet and dry adhesion between surfaces. KTH Royal Institute of Technology, StockholmGoogle Scholar
  9. 9.
    Petzold G, Lunkwitz K (1995) The interaction between polyelectrolyte complexes made from poly(dimethyldiallylammonium chloride) (PDMDAAC) and poly(maleic acid-co-α-methylstyrene) (P(MS-α-MeSty)) and cellulosic materials. Colloids Surf A 98:225–233CrossRefGoogle Scholar
  10. 10.
    Bungenberg de Jong HG, Kryut HR (1929) Coacervation (partial miscibility in colloid systems). Proc Acad Sci Amsterdam 32:849Google Scholar
  11. 11.
    Dautzenberg H (2001) Polyelectrolyte complex formation in highly aggregating systems: methodical aspects and general tendencies. In: Radeva T (ed) Physical chemistry of polyelectrolytes. Dekker, New YorkGoogle Scholar
  12. 12.
    Fleer GJ, Cohen Stuart MA, Scheutjens JMHM et al (1993) Electrostatic effects: charged surfaces and polyelectrolyte adsorption. In: Polymers at interfaces. Chapman & Hall, LondonGoogle Scholar
  13. 13.
    Norde W (2003) Colloids and interfaces in life science. Marcel Dekker, New YorkCrossRefGoogle Scholar
  14. 14.
    Van de Ven TGM (1989) Colloidal hydrodynamics. Academic, San DiegoGoogle Scholar
  15. 15.
    Shubin V, Linse P (1995) Effect of electrolytes on adsorption of cationic polyacrylamide on silica: ellipsometric study and theoretical modeling. J Phys Chem 99:1285–1291CrossRefGoogle Scholar
  16. 16.
    Linse P, Wennerström H (2012) Adsorption versus aggregation. Particles and surface of the same material. Soft Matter 8:2486–2493CrossRefGoogle Scholar
  17. 17.
    Ondaral S, Ankerfors C, Ödberg L et al (2010) Surface-induced rearrangement of polyelectrolyte complexes: influence of complex composition on adsorbed layer properties. Langmuir 26:14606–14614CrossRefGoogle Scholar
  18. 18.
    Alince B, Kinkal J, Bednar F et al (2002) The role of “free charge” in the deposition of latex particles onto pulp fibers. In: Daniels ES, Sudol ED, El-Aasser MS (eds) ACS Symp Ser. American Chemical Society, Washington, DCGoogle Scholar
  19. 19.
    Gärdlund L, Wågberg L, Gernandt R (2003) Polyelectrolyte complexes for surface modification of wood fibres II. Influence of complexes on wet and dry strength of paper. Colloids Surf A 218:137–149CrossRefGoogle Scholar
  20. 20.
    Biggs S, Sakai K, Addison T et al (2007) Layer-by-layer formation of smart particle coatings using oppositely charged block copolymer micelles. Adv Mater 19:247–250CrossRefGoogle Scholar
  21. 21.
    Toomey R, Mays J, Holley DW et al (2005) Adsorption mechanisms of charged, amphiphilic diblock copolymers: the role of micellization and surface affinity. Macromolecules 38:5137–5143CrossRefGoogle Scholar
  22. 22.
    Wittmer J, Joanny J-F (1993) Charged diblock copolymers at interfaces. Macromolecules 26:2691–2697CrossRefGoogle Scholar
  23. 23.
    Kramer G, Somasundaran P (2004) Fluorescence and ESR studies of the conformational behavior of oppositely charged polyelectrolytes at solid/liquid interfaces. J Colloid Interface Sci 273:115–120CrossRefGoogle Scholar
  24. 24.
    Hubbe MA, Moore SM, Lee SY (2005) Effects of charge ratios and cationic polymer nature on polyelectrolyte complex deposition onto cellulose. Ind Eng Chem Res 44:3068–3074CrossRefGoogle Scholar
  25. 25.
    Saarinen T, Österberg M, Laine J (2008) Adsorption of polyelectrolyte multilayers and complexes on silica and cellulose surfaces studied by QCM-D. Colloids Surf A 330:134–142CrossRefGoogle Scholar
  26. 26.
    Norgren M, Gärdlund L, Notley SM et al (2007) Smooth model surfaces from lignin derivatives. II. Adsorption of polyelectrolytes and PECs monitored by QCM-D. Langmuir 23:3737–3743CrossRefGoogle Scholar
  27. 27.
    Wågberg L, Lindström T (1987) Some fundamental aspects on dual component retention aid systems. Nord Pulp Pap Res J 2:49–55CrossRefGoogle Scholar
  28. 28.
    Lofton MC, Moore SM, Hubbe MA et al (2005) Deposition of polyelectrolyte complexes as a mechanism for developing paper dry strength. Tappi J 4:3–8Google Scholar
  29. 29.
    Koljonen K, Vainio A, Hiltunen E et al (2003) The effect of polyelectrolyte adsorption on the strength properties of paper made from mixtures of mechanical and chemical pulps. In: Proceedings 5th International Paper and Coating Chemistry Symposium, Montreal, Canada, June 2003. Pulp and Paper Research Institute of CanadaGoogle Scholar
  30. 30.
    Vainio A, Paulapuro H, Koljonen K et al (2006) The effect of drying stress and polyelectrolyte complexes on the strength properties of paper. J Pulp Pap Sci 32:9–13Google Scholar
  31. 31.
    Heermann ML, Welter SR, Hubbe MA (2006) Effects of high treatment levels in a dry-strength additive program based on deposition of polyelectrolyte complexes: how much glue is too much? Tappi J 5:9–14Google Scholar
  32. 32.
    Hubbe MA (2005) Dry-strength development by polyelectrolyte complex deposition onto non-bonding glass fibres. J Pulp Pap Sci 31:159–166Google Scholar
  33. 33.
    Lindström T (1989) Some fundamental chemical aspects on paper forming. In: Punton V and Baker CF (eds) Fundamentals of papermaking: transactions 9th fundamental research symposium, Cambridge, Sept 1989. Mechanical Engineering Publications, LondonGoogle Scholar
  34. 34.
    Andersson K, Lindgren E (1996) Important properties of colloidal silica in microparticulate systems. Nord Pulp Pap Res J 11:15–21CrossRefGoogle Scholar
  35. 35.
    Agarwal M, Lvov Y, Varahramyan K (2006) Conductive wood microfibres for smart paper through layer-by-layer nanocoating. Nanotechnology 17:5319–5325CrossRefGoogle Scholar
  36. 36.
    Agarwal M, Xing Q, Shim BS et al (2009) Conductive paper from lignocellulose wood microfibers coated with a nanocomposite of carbon nanotubes and conductive polymers. Nanotechnology 20: 215602Google Scholar
  37. 37.
    Renneckar S, Zhou Y (2009) Nanoscale coatings on wood: polyelectrolyte adsorption and layer-by-layer assembled film formation. ACS Appl Mater Interfaces 1:559–566CrossRefGoogle Scholar
  38. 38.
    Lindström T, Söremark C, Westman L (1977) The influence on paper strength of dissolved and colloidal substances in the white water. Svensk Papperstid 80:341–345Google Scholar
  39. 39.
    Nylund J, Byman-Fagerholm H, Rosenholm JB (1993) Physico-chemical characterization of colloidal material in mechanical pulp. Nord Pulp Pap Res J 8:280–283CrossRefGoogle Scholar
  40. 40.
    Li P, Pelton R (1992) Wood pulp washing. 1. Complex formation between kraft lignin and cationic polymers. Colloids Surf 64:217–222CrossRefGoogle Scholar
  41. 41.
    Li P, Pelton R (1992) Wood pulp washing. 2. Displacement washing of aqueous lignin from model beds with cationic polymer solutions. Colloids Surf 64:223–234CrossRefGoogle Scholar
  42. 42.
    Ström G (1984) For better or for worse: polyelectrolyte complexes in the stock. Svensk Papperstid 87:14–16, 19–20Google Scholar
  43. 43.
    Ström G, Barla P, Stenius P (1979) The formation of lignin sulphonate-polyethyleneimine complexes and its influence on pulp drainage. Svensk Papperstid 82:408–413Google Scholar
  44. 44.
    Ström G, Barla P, Stenius P (1982) The effect on pine xylan on the use of some polycations as retention and drainage aids. Svensk Papperstid 85:R100–R106Google Scholar
  45. 45.
    Ström G, Barla P, Stenius P (1985) The formation of polyelectrolyte complexes between pine xylan and cationic polymers. Colloids Surf 13:193–207CrossRefGoogle Scholar
  46. 46.
    Ström G, Stenius P (1981) Formation of complexes, colloids and precipitates in aqueous mixtures of lignin sulfonate and some cationic polymers. Colloids Surf 2:357–371CrossRefGoogle Scholar
  47. 47.
    Ödberg L, Ström G (1983) ESCA studies of retention and dewatering aids. The adsorption of polymin SN and polymin SN-lignosulfonate complexes on cellulose. Svensk Papperstid 86:R141–R145Google Scholar
  48. 48.
    Rojas OJ, Neuman RD (1999) Adsorption of polysaccharide wet-end additives in papermaking systems. Colloids Surf A 155:419–432CrossRefGoogle Scholar
  49. 49.
    Vanerek A, van de Ven TGM (2006) Coacervate complex formation between cationic polyacrylamide and anionic sulfonated kraft lignin. Colloids Surf A 273:55–62CrossRefGoogle Scholar
  50. 50.
    Ankerfors C, Ondaral S, Wågberg L et al (2010) Using jet mixing to prepare polyelectrolyte complexes: complex properties and their interaction with silicon oxide surfaces. J Colloid Interface Sci 351:88–95CrossRefGoogle Scholar
  51. 51.
    Johnson BK, Prud'homme RK (2003) Mechanism for rapid self-assembly of block copolymer nanoparticles. Phys Rev Lett 91:118302CrossRefGoogle Scholar
  52. 52.
    Petzold G, Schwartz S (2013) Polyelectrolyte complexes in flocculation applications. Adv Polym Sci. doi: 10.1007/12_2012_205
  53. 53.
    Gärdlund L, Forsström J, Andreasson B et al (2005) Influence of polyelectrolyte complexes on the strength properties of papers from unbleached kraft pulps with different yields. Nord Pulp Pap Res J 20:36–42CrossRefGoogle Scholar
  54. 54.
    Gärdlund L, Norgren M, Wågberg L et al (2007) The use of polyelectrolyte complexes (PECs) as strength additives for different pulps used for production of fine paper. Nord Pulp Pap Res J 22:210–216CrossRefGoogle Scholar
  55. 55.
    Espy HH (1995) The mechanism of wet-strength development in paper: a review. Tappi J 78:90–99Google Scholar
  56. 56.
    Johnson BK, Prud'homme RK (2003) Chemical processing and micromixing in confined impinging jets. AIChE J 49:2264–2282CrossRefGoogle Scholar
  57. 57.
    Eriksson M, Notley SM, Wågberg L (2005) The influence on paper strength properties when building multilayers of weak polyelectrolytes onto wood fibers. J Colloid Interface Sci 292:38–45CrossRefGoogle Scholar
  58. 58.
    Lingström R, Wågberg L (2008) Polyelectrolyte multilayers on wood fibers: influence of molecular weight on layer properties and mechanical properties of papers from treated fibers. J Colloid Interface Sci 328:233–242CrossRefGoogle Scholar
  59. 59.
    Ankerfors C, Lingström R, Wågberg L et al (2009) A comparison of polyelectrolyte complexes and multilayers: their adsorption behaviour and use for enhancing tensile strength of paper. Nord Pulp Pap Res J 24:77–86CrossRefGoogle Scholar
  60. 60.
    Feng X, Pouw K, Leung V et al (2007) Adhesion of colloidal polyelectrolyte complexes to wet cellulose. Biomacromolecules 8:2161–2166CrossRefGoogle Scholar
  61. 61.
    Feng X, Pelton R, Leduc M (2006) Mechanical properties of polyelectrolyte complex films based on polyvinylamine and carboxymethyl cellulose. Ind Eng Chem Res 45:6665–6671CrossRefGoogle Scholar
  62. 62.
    Xiao L, Salmi J, Laine J et al (2009) The effects of polyelectrolyte complexes on dewatering of cellulose suspension. Nord Pulp Pap Res J 24:148–157CrossRefGoogle Scholar
  63. 63.
    Arzt E, Gorb S, Spolenak R (2003) From micro to nano contacts in biological attachment devices. Proc Natl Acad Sci USA 100:10603–10606CrossRefGoogle Scholar
  64. 64.
    Lamblet M, Verneuil E, Vilmin T et al (2007) Adhesion enhancement through micropatterning at polydimethylsiloxane-acrylic adhesive interfaces. Langmuir 23:6966–6974CrossRefGoogle Scholar
  65. 65.
    Bakker HE, Lindström SB, Sprakel J (2012) Geometry- and rate-dependent adhesive failure of micropatterned surfaces. J Phys Condens Matter 24:065103Google Scholar
  66. 66.
    Torgnysdotter A, Kulachenko A, Gradin P et al (2007) The link between the fiber contact zone and the physical properties of paper: a way to control paper properties. J Compos Mater 41:1619–1633CrossRefGoogle Scholar
  67. 67.
    Ankerfors C, Johansson E, Pettersson T et al (2013) Use of polyelectrolyte complexes and multilayers from polymers and nanoparticles to create sacrificial bonds between surfaces. J Colloid Interface Sci 391:28–35CrossRefGoogle Scholar
  68. 68.
    Bartlett MD, Croll AB, King DR et al (2012) Looking beyond fibrillar features to scale gecko-like adhesion. Adv Mater 24:1078–1083CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  1. 1.Swerea KIMABKistaSweden
  2. 2.Department of Fibre and Polymer TechnologyKTH Royal Institute of TechnologyStockholmSweden
  3. 3.The Wallenberg Wood Science Centre (WWSC)KTH Royal Institute of TechnologyStockholmSweden

Personalised recommendations