Mid Sweden University

Silica surfaces were consecutively treated with copolymers of cationic and anionic polyacrylamides (C-PAM and A-PAM, respectively) and the layer-by-layer build-up was continuously monitored with the aid of stagnation point adsorption reflectometry (SPAR). Four different charge densities of the cationic polymer and one charge density of the anionic polymer were studied. The solid substrate used in the investigation was an oxidized Si wafer, the charge of which was varied by performing the measurements at different pH. Adsorption measurements were performed both in deionized water and with a background electrolyte concentration of 0.01 M NaCl The results show that the adsorption of C-PAM at pH 6 was dominated by electrostatic interactions. However, a significant nonionic contribution to the adsorption of C-PAM on SiO2 was detected-when the results of adsorption measurements conducted in deionized water and in 0.01 M NaCl were compared. At pH 9, the adsorption of C-PAM onto SiO2 was found to be geometrically restricted since the adsorption stoichiometry between the polymer charges and the charges on the surface was less than I irrespective of the charge of the C-PAM. Adsorption of the A-PAM onto the C-PAM covered surface increases as a function of the adsorbed charges in the first layer. Experiments showed that it was possible to form multilayers of polyelectrolytes on the SiO2 surface provided the charge of the C-PAM was high enough. The critical charge of the polyelectrolyte for the formation of multilayers was also dependent on the charge of the substrate; that is, the lower the surface charge the higher the critical charge of the C-PAM. The substrate affected the amount of polyelectrolyte adsorbed up to the fifth layer. For further layers there was almost a stoichiometric relationship between the charges of the polyelectrolytes in consecutive layers. Results from studies of the formed multilayers with a quartz crystal microbalance (QCM-D) indicated that there was a close correlation between energy dissipation into the multilayers and a decrease in the adsorption as detected with SPAR. This in turn indicates that a decrease in the reflectometer signal does not necessarily indicate a decrease in adsorption.

Polyelectrolyte multilayers of cationic and anionic starch have been used to enhance the strength properties of paper. All starches used in this investigation had a degree of substitution around 0.065. Optical reflectometry showed that a combination of cationic and anionic starch could form polyelectrolyte multilayers onto silicon oxide surfaces. The same combination of starches was then applied to unbeaten, bleached softwood kraft fibres to form three layers, i.e. a cationic/anionic/cationic starch combination. The results showed a significant increase in the paper strength properties in terms of tensile index, strain at break, and Scott Bond. The adsorbed amount of starch in the sheets, determined using an enzymatic method, was found to increase with each successive starch treatment. The increased paper strength was not only due to the increase in adsorbed amount of starch; rather, the chemical composition of the starch was also important. Cationic starch with high amylose content had a more positive effect on the paper strength properties. Furthermore, it was observed that anionic starch, despite being adsorbed in large amounts, did not contribute to the increase in tensile strength or strain at break to the same extent as did cationic starch. However, the out-of-plane properties, measured as Scott Bond properties, increased with the adsorbed amount, regardless of the chemical composition of the starch used in the outermost layer.

The construction of alternating multilayers of cationic potato starch and anionic carboxymethylcellulose(CMC) was investigated in two parts. In the first part, stagnation point adsorption reflectometry (SPAR) showed that the chosen chemicals formed polyelectrolyte multilayers (PEM)upon adsorption to the silicon oxide surface. This was in accordance with earlier work. The chosen polyelectrolytes adsorbed to similar extents on the silicon oxide surface and recharged the surface enough to allow for adsorption of a consecutive layer. In the second part, the multilayer concept was tested on 80/20,20/80% of total in mixture of mixed spruce CTMP and bleached chemical pulp in order to enhance the sheet strength properties of a typical packaging board furnish.. The multilayers yielded a significant improvement in Scott Bond values and tensile index and a marginal improvement in tensile stiffness index. The Scott Bond values were improved more than 150% for papers prepared from a furnish consisting of 80% spruce CTMP and 20% chemical pulp. Polyelectrolyte multilayers treatment also led to a slight densification of the sheets, but the polyelectrolyte multilayers treatment resulted in a more favourable density/strength relationship than that achieved with a change in the amount of chemical pulp.

Polyelectrolyte multilayers (PEM) consisting of cationic starch and anionic carboxymethylcellulose (CMC) have been applied to different pulp fibres in order to enhance the out-of-plane sheet strength properties of a typical packaging board furnish. An unbleached softwood chemical pulp was treated with multilayers consisting of two layers of cationic starch and one layer of CMC, and then mixed with different mechanical and chemimechanical pulps. Hand sheets were prepared with the aid of the Rapid Köthen sheet former from stocks consisting of 20% treated chemical pulp and 80% mechanical or chemimechanical pulp, which was either PGW from spruce, HT-CTMP from spruce or birch, or a standard spruce CTMP. Multilayer treatment significantly improved Scott Bond values and in some cases improved the tensile index, with the achieved effects being significantly larger than the effects of applying starch alone. Positive effects were obtained by treating only 20% of the furnish, showing a very high efficiency of the adsorbed multilayers. Compared to earlier work, one important finding was that the PEM treatment should preferably be applied only to the chemical pulp and not on the entire stock. It was possible to increase the out-of-plane strength properties, measured as Scott Bond values, with just a very small increase in density of the sheets. Multilayer treatment of the chemical pulp improved the joint strength between the fibres while maintaining the high bulk of the sheets prepared from the stiff mechanical and chemimechanical fibres.

In this study a sack paper furnish was used. It consisted of a high-consistency kraft pulp refined in either an atmospheric pressure or a pressurized system. The pulps were subsequently low-consistency refined in an Escher-Wyss laboratory refiner to 17.5-20.5 SR. Ordinary ISO sheets and freely dried sheets were manufactured from these pulp samples to serve as reference sheets. The laboratory sheets made of pulp from the pressurized system had a higher strain at break and tensile energy adsorption index but a lower tensile index than sheets made of pulp from a conventional atmospheric highconsistency refiner. These sheets were subject to a polyelectrolyte multilayer treatment to increase the interaction between the fibres, thus enhancing the paper strength properties. The polyelectrolyte multilayers (PEM) were applied by sequentially treating fibres from an unbleached kraft pulp for sack paper production with cationic starch and anionic carboxymethyl cellulose. The multilayer treatment was only applied to 50% of the stock and both ordinary ISO sheets and freely dried sheets were prepared with one and three layers of polyelectrolyte. Evaluation of the strength properties of the sheets showed that the addition of only one layer of starch increased strain at break, tensile index, tensile energy adsorption index, and out-of-plane properties measured as Scott-bond values. Using the multilayer technique created large increases in Scott-bond, a measure of the internal bonding of the sheets. The achieved effects were significantly larger than those usually achieved by applying starch alone to enhance the out-of plane strength properties. Also, the density increased considerably when the third layer was applied, for both ISO and freely dried sheets, though the tensile strength was enhanced significantly only in the freely dried sheets.