Formation and properties of polyelectrolyte multilayers on wood fibres :  influence on paper strength and fibre wettability

Abstract: The work in this licentiate thesis examines the adsorption of polyelectrolyte multilayers (PEM) onto wood fibres as a new way to influence the properties of the fibre surfaces and hence the fibres. Fundamental aspects of PEM formation on wood fibres have been studied, and discussed in terms of paper strength and wood fibre wettability.PEMs have been formed from three different polymer systems: 1) two strong polyelectrolytes (i.e., fully charged over a wide pH range), polydimethyldiallylammonium chloride (PDADMAC) and polystyrene sulphonate (PSS); 2) polyethylene oxide (PEO) and polyacrylic acid (PAA), formed at low pH and held together by hydrogen bonding; and 3) two weak polyelectrolytes, polyallylamine hydrochloride (PAH) and polyacrylic acid (PAA). The PEMs formed from PDADMAC/PSS and PEO/PAA were studied using Stagnation Point Adsorption Reflectometry (SPAR), with SiO2 as the substrate. This was done to establish the formation of PEMs and, using PDADMAC/PSS, also to predict the influence of salt concentration during PEM formation. The amount of PDADMAC/PSS adsorbed was found to increase with salt concentration up to approximately 0.1 M NaCl. The formation of PEMs from PAH/PAA has already been studied in terms of structure; amount adsorbed, and influence on paper strength.Sheets were formed from fibres treated with either PDADMAC/PSS or PEO/PAA PEMs and tested to determine paper tensile strength. Both PEM systems increased the tensile index and strain at break in the range of 100% when approximately 10 layers had been adsorbed. After several PEM layers had been adsorbed, the sheets made of fibres treated with PDADMAC/PSS differed in tensile strength depending on the polymer adsorbed in the outermost layer. A higher tensile strength was detected when PDADMAC rather than PSS was adsorbed in the outermost layer. Sheets made of fibres treated with PEO/PAA displayed a linear increase in strength, independent of which polymer that was adsorbed in the outermost layer.The amount of adsorbed PDADMAC/PSS, as analysed using nitrogen and sulphur analysis, respectively, increased linearly, but with a higher amount adsorbed in the first layer. A comparison of the adsorption onto the SiO2-surfaces (SPAR-measurements) and fibres shows some differences. This is apparent both regarding the adsorption in the first layer and in the change in adsorbed amount with salt concentration. Despite this, one can conclude that SiO2 and wood fibres show very similar trends, and that SiO2 can be used as a convenient model surface in predicting PEM formation on wood fibres.Individual fibres were also partially treated using a Dynamic Contact Angle Analyser, and the treated and untreated parts were analysed in terms of wettability and surface structure. The differences in wettability are significant, depending on the polymer system used and, with PAH/PAA PEMs, the pH strategy show a large influence in wettability. PDADMAC/PSS and PAH/PAA PEMs both had a large influence on wettability, depending on the polymer adsorbed in the outermost layer, wettability being lower when the cationic polymer was adsorbed in the outermost layer. With the PEO/PAA system, however, the polymer adsorbed in the outermost layer caused no detectable difference. These results, when compared against the paper strength results, indicate that the strongest sheets are formed of the fibres with the lowest wettability. This may be explained in terms of wet adhesion: since the fibre networks are formed in water, lower wettability would give a stronger force between the fibres during consolidation, resulting in a greater contact area and thus probably a stronger dry adhesion between the fibres in the formed sheet. This is furthermore also supported by wet adhesion measurements using Atomic Force Microscopy where PEMs formed from PAH/PAA, show that the pull-off force is increased when PAH is adsorbed in the outermost layer, compared to when PAA is adsorbed in the outermost layer.