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  • 1.
    Johansson, Erik
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Lundström, Lisa
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Norgren, Magnus
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Adsorption Behavior and Adhesive Properties of Biopolyelectrolyte Multilayers formed from Cationic and Anionic Starch2009In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 10, no 7, p. 1768-1776Article in journal (Refereed)
    Abstract [en]

    Cationic starch (D.S. 0.065) and anionic starch (D.S. 0.037) were used to form biopolyelectrolyte multilayers. The influence of the solution concentration of NaCl on the adsorption of starch onto silicon oxide substrates and on the formation of multilayers was investigated using stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D). The wet adhesive properties of the starch multilayers were examined by measuring pull-off forces with the AFM colloidal probe technique. It was shown that polyelectrolyte multilayers (PEM) can be successfully constructed from cationic starch and anionic starch at electrolyte concentrations of 1 mM NaCl and 10 mM NaCl. The water content of the PEMs was approximately 80% at both electrolyte concentrations. However, the thickness of the PEMs formed at 10 mM NaCl was approximately twice the thickness formed at I mM NaCl. The viscoelastic properties of the starch PEMs, modeled as Voigt elements, were dependent on the polyelectrolyte that was adsorbed in the outermost layer. The PEMs appeared to be more rigid when capped by anionic starch than when capped by cationic starch. The wet adhesive pull-off forces increased with layer number and were also dependent oil the polyelectrolyte adsorbed in the outermost layer. Thus, starch PEM treatment has a large potential for increasing the adhesive interaction between solid substrates to levels higher than can be reached by a single layer of cationic starch.

  • 2.
    Lundström, Lisa
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Polyelectrolyte multilayers of cationic and anionic starch and their use for improving the strength of papers made from mechanical pulps2009Licentiate thesis, comprehensive summary (Other academic)
    Abstract [en]

    Graphic paper is experiencing severe competition from other materials and, most of all, from other media. This means there is a great need to improve paper quality while reducing raw material and production costs. Polyelectrolyte multilayer (PEM) treatment (i.e., consecutively adding cationic and anionic polyelectrolytes to the charged surface of wood fibres and fines, to form layers of these polyelectrolytes on the fibres/fines) has in recent years been found to offer great potential both to introduce new properties and to improve the mechanical properties of papers made of the treated fibres.

    The main objective of this thesis was to develop a strategy for the PEM treatment of cationic and anionic starch to improve the mechanical properties of paper made of thermomechanical pulp (TMP), since PEM treatment of fibres has displayed great potential to improve the mechanical properties of sheets made of chemical pulp. Mechanical pulp, however, has a large fine material content. Since the fine material is highly charged, polyelectrolyte consumption would be unacceptably high if the entire pulp were PEM treated, so we applied PEM treatment only to a fibre fraction of the pulps in most trials in the present work. The polyelectrolytes used for PEMs have so far mostly been well-defined, expensive ones unsuitable for use in standard paper grades; to develop a more economically realistic alternative, we used cationic and anionic starches.

    PEM formation on SiO2 surfaces from three differently charged cationic and anionic starches was first evaluated at three different salt levels using quartz crystal microbalance with dissipation (QCM-D) and stagnation point adsorption reflectometry (SPAR). The starch combinations displaying the highest potential for stable PEM formation at higher salt concentrations were then evaluated on an entire TMP pulp, as well as on a fraction of the pulp to reduce the amount of starch needed for PEM formation.

    The results indicate that it is possible to form PEMs from cationic and anionic starch on a SiO2 surface. The charge density, salt concentration, and combination of starches all influenced PEM formation. PEM formation on mechanical fibres produced large improvements in the mechanical properties of the sheets made of the treated fibres, and the tensile index, stretch-at-break, Z-strength, and Scott bond values all increased. Fractionating the pulp and PEM treating only a fraction of the pulp, the long fibre and middle fraction, produced large decreases in the amount of starch needed and large improvements in the mechanical properties of the sheets when no fine material was subsequently added. As untreated fine material was subsequently added, the improvement in mechanical properties decreased. PEM formation produced almost no reduction in formation and only a slight increase in sheet density.

  • 3.
    Lundström-Hämälä, Lisa
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Johansson, Erik
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Polyelectrolyte Multilayers from Cationic and Anionic Starch: Influence of Charge Density and Salt Concentration on the Properties of the Adsorbed Layers2010In: Starke (Weinheim), ISSN 0038-9056, E-ISSN 1521-379X, Vol. 62, no 2, p. 102-114Article in journal (Refereed)
    Abstract [en]

    The purpose of the present work was for identify limits for the formation of stable polyelectrolyte multilayers (PEMs) from cationic and anionic starches (with degrees of substitution of 0.04-0.09) on SiO2 surfaces, taking account of the effect of the charge density of the starches and the salt concentration in the surrounding water phase. The experiments were performed at a pH of 6.3 using stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D). From these experiments it was concluded that it is possible to form PEMs by the adsorption of oppositely charged starches on SiO2 surfaces; it was also found that adsorption of the first layer is controlled both by electrostatic, non-ionic interactions and by pure steric restrictions, Le, geometrical restrictions, at the surface. The results also indicate that the charge density of the starch must exceed a certain value to allow multilayer formation and that this critical charge density increases with increasing salt concentration. The combination of charge densities of the cationic/anionic starches was also found to influence the adsorption behaviour, and the formed polyelectrolyte multilayers had a high water content of 69-92%.

  • 4. Lundström-Hämälä, Lisa
    et al.
    Lindgren, Johan
    Svensson-Rundlöf, Eva
    Sennerfors, Therese
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    The adsorption of polyelectrolyte multilayers (PEM) of starch on mechanical pulps for improved mechanical paper properties2009In: Nordic Pulp & Paper Research Journal, ISSN 0283-2631, E-ISSN 2000-0669, Vol. 24, no 4, p. 459-468Article in journal (Refereed)
    Abstract [en]

    In the present work, the long fibre and middle fibre fraction of a thermomechanical pulp (TMP) was treated with polyelectrolyte multilayers (PEMs) of cationic and anionic starch and sheets were made from both the treated and untreated fractions. In separate experiments, different amounts of untreated fines were added to the PEM-treated fraction before sheets were prepared, and the results were also compared with PEM treatment of the entire pulp containing 17% fines before sheet preparation. The PEMs were made of two different combinations of starch, two cationic potato starches with DS values of 0.06 and 0.09, both in combination with an anionic potato starch with a DS of 0.04, at 0.010 M NaCl and pH 6.3. Sheets were formed using the Rapid Kothen sheet former and the resulting mechanical and optical sheet properties were evaluated. Four-layer PEM treatment of the long fibre and middle fraction resulted in significant improvements in in-plane and out-of-plane mechanical properties. However, a subsequent fines addition reduced the effect of the PEMs, and this is explained by a blocking of the necessary PEM interaction with the treated TMP long fibre and middle fraction by the subsequently added fines. PEM treatment of the entire pulp increased the amount of starch needed for PEM treatment, but improved the in-plane and out-of-plane mechanical properties compared with those of sheets prepared from a PEM-treated long fibre and middle fraction with a subsequent addition of fine material. The increase in the tensile index for sheets made from a PEM-treated long fibre and the middle fraction without a subsequent fines addition, however, was much larger.

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