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Abstract: This paper compares the influence of the molecular weight of polylelectrolytes forming polyelectrolyte multilayers (PEM) on wood fibers on adhesion and paper strength. Sheets were made from fibers treated with poly(allylamine hydrochloride) (PAH)/poly(acrylic acid) (PAA) of molecular mass 70,000 and 240,000, respectively, and of poly(dimethyldiallylammonium chloride) (PDADMAC)/poly(styrene sulfonate) (PSS) of molecular mass 30,000 and 80,000, respectively. The results were compared to what has recently been reported for PEM formation on fibers using a low-molecular-mass combination of PAH and PAA and a high-molecular-mass combination of PDADMAC/PSS. There was a less significant improvement in the case of the low-molecular-mass PDADMAC/PSS and the high-molecular-mass PAH/PAA. The adsorbed amounts of PAH and PDADMAC were also determined, showing a lower adsorbed amount of the low-molecular-mass PAH than of the high-molecular-mass PDADMAC. The amount of low-molecular-mass PDADMAC was similar to that found for high-molecular-mass PDADMAC/PSS. Individual fibers were partly treated and studied, showing a less significant decrease in wettability with low-molecular-mass PDADMAC/PSS than with the high-molecular-mass combination. The effect of the molecular weight on the adhesion was discussed in terms of the structure and wettability of the PEMs. [Copyright &y& Elsevier]

Abstract: The conformation of cationic polyelectrolytes preadsorbed on macroscopic silica surfaces was studied before and after addition of colloidal silica (CS) and compared to the fixation capacity of CS. The study included two polyelectrolytes of equal charge density, cationic polyacrylamide and cationic dextran. Adsorbed amounts were determined with stagnation point adsorption reflectometry (SPAR) and quartz crystal microgravimetry (QCM). Unsaturated layers of polyelectrolyte were formed in SPAR by stopping the adsorption at a fractional coverage relative to saturation adsorption. These layers were probed by secondary saturation adsorption of colloidal silica (CS). At low salt concentrations a high fractional coverage of polyelectrolyte was required to attain adsorption of CS, while significant adsorption of CS was found also for low fractional coverages of polyelectrolyte at salt concentrations above 10 mM NaCl. Saturation adsorption of cationic polyacrylamide (CPAM) and cationic dextran (Cdextran) onto the silica surface was found to be similar, while the secondary adsorption of CS was significantly higher onto preadsorbed CPAM compared with Cdextran. The QCM and SPAR data together indicated that the adsorbed layer of Cdextran was thinner than CPAM, and that a loose, expanded layer was formed after adsorption of CS on CPAM but not on Cdextran. [Copyright &y& Elsevier]

Abstract: Polydimethyldiallylammonium chloride (PDADMAC) and polystyrene sulfonate (PSS) have been used to build-up polyelectrolyte multilayers (PEMs) on chemical soft wood fibres and on SiO2 at various electrolyte concentrations. Adsorption onto SiO2 was studied using a stagnation point adsorption reflectometer (SPAR), and the adsorbed amount of PDADMAC and PSS on the fibres was determined using nitrogen analysis and Schöniger burning, respectively. The adsorption onto the two substrates was then compared. Paper testing showed that the tensile index (TI) increased by about 90% when 11 layers had been adsorbed, and that there was a correlation between the adsorbed amount and the increase in TI. It was also shown that the particular polymer present in the outermost layer significantly influenced the TI, and that PDADMAC produced a higher TI. A correlation between the adsorbed amount and the TI was also found. Individual fibres were partly treated with a PEM and analysed using a dynamic contact angle analyser (DCA) and environmental scanning electron microscopy (ESEM). [Copyright &y& Elsevier]

Abstract: The influence of mixing procedure on the properties of polyelectrolyte complexes (PECs) was investigated using two complexation techniques, polyelectrolyte titration and jet mixing, the latter being a new method for PEC preparation. For the low-molecular-weight polyelectrolytes polyacrylic acid (PAA) and polyallyl amine hydrochloride (PAH), shorter mixing times produced smaller PECs, whereas for higher molecular weights of the same polyelectrolytes, PEC size first decreased with decreasing mixing time to a certain level, after which it started increasing again. This pattern was likely due to the diffusion-controlled formation of “pre-complexes”, which, in the case of low-molecular-weight polymers, occurs sufficiently quickly to form stable complexes; when polyelectrolytes are larger, however, non-equilibrium pre-complexes, more prone to aggregation, are formed. Comparing the techniques revealed that jet mixing produced smaller complexes, allowing PEC size to be controlled by mixing time, which was not the case with polyelectrolyte titration. Higher polyelectrolyte concentration during jet mixing led to the formation of larger PECs. It was also demonstrated that PEC size could be changed after preparation: increasing the pH of the PEC dispersion led to an irreversible increase in PEC size, whereas lowering the pH did not influence PEC size. The adsorption behavior of PECs formed from weak polyelectrolytes on model substrates was studied using QCM-D, SPAR, and AFM imaging; the results indicated that increasing the pH increased the amount of PECs adsorbed to model surfaces. However, the amount of PECs adsorbed to the model surfaces was low compared with other systems in all studied cases. [ABSTRACT FROM AUTHOR]

Abstract: Polyallylamine hydrochloride (PAH) and polyacrylic acid (PAA) have been used to build up polyelectrolyte multilayers (PEM) on wood fibres and on silicon oxide surfaces, under various pH conditions. Consecutive adsorption onto silicon oxide surfaces of PAH and PAA were studied using stagnation point adsorption reflectometry, and the results showed a steady build-up of multilayers. Furthermore, by altering pH, the build-up of the multilayer could be made either linear or exponential in terms of adsorbed amount. Nitrogen analysis of sheets prepared from modified fibres showed that the adsorbed amount of PAH increased throughout PEM build-up, the amount of increase depending on pH during adsorption. Strength measurements of the sheets, i.e., stress at break and strain at break, showed significant improvements ranging from 60 to 200%, depending on both pH during adsorption and type of polyelectrolyte in the outer layer. A good correlation between the adsorbed amount of PAH and the improved strength properties of the paper was also found. [Copyright &y& Elsevier]

Macroscopic beads of water-based gels consisting of uncharged and partially charged β-(1,4)- d -glucan polymers were developed to be used as a novel model material for studying the water induced swelling of the delignified plant fiber walls. The gel beads were prepared by drop-wise precipitation of solutions of dissolving grade fibers carboxymethylated to different degrees. The internal structure was analyzed using Solid State Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance and Small Angle X-ray Scattering showing that the internal structure could be considered a homogeneous, non-crystalline and molecularly dispersed polymer network. When beads with different charge densities were equilibrated with aqueous solutions of different ionic strengths and/or pH, the change in water uptake followed the trends expected for weak polyelectrolyte gels and the trends found for cellulose-rich fibers. When dried and subsequently immersed in water the beads also showed an irreversible loss of swelling depending on the charge and type of counter-ion which is commonly also found for cellulose-rich fibers. Taken all these results together it is clear that the model cellulose-based beads constitute an excellent tool for studying the fundamentals of swelling of cellulose rich plant fibers, aiding in the elucidation of the different molecular and supramolecular contributions to the swelling. [ABSTRACT FROM AUTHOR]

Abstract: In this study, particle polyelectrolyte complexes (PPECs) were formed by mixing cationic polyacrylamide (CPAM) and silica nanoparticles using the jet mixing technique. Within certain limits, the size of the formed PPECs could be controlled. The aim was to prepare PPECs with embedded sacrificial bonds, similar to those found in bones. Examination of PPEC adsorption to silica model surfaces indicated that smaller PPECs adsorbed to a higher level than larger ones, due to the higher diffusion speed of smaller complexes. Adsorption studies of the same components as in the PPECs, but arranged in multilayers, that is, particle polyelectrolyte multilayers (PPEMs), indicated a stable, gradual build-up of material on the surface with smaller nanoparticles, whereas PPEMs comprising elongated nanoparticles appeared to be more loosely adsorbed onto the surface when the nanoparticles were in the outer layer, due to repulsive forces within the adsorbed layer. The AFM colloidal probe technique was used to study the interaction between surfaces treated with PPECs, multilayers, or polyelectrolyte complexes (PECs). The results showed that the expected long-range disentanglement could be achieved with PPECs but that the pull-off forces were generally low. Treatment with PPEMs comprising the same polymer and nanoparticle components produced higher pull-off values, together with disentanglement behaviour, possibly due to better contact between the surfaces. Adhesion experiments with polymer PECs showed significantly higher pull-off values than with the PPECs, probably due to polymer interdiffusion across the surface boundary. [Copyright &y& Elsevier]