The effects of charge density, pH, and salt concentration on polyelectrolyte adsorption onto the oxidized surface of silicon wafers were studied using stagnation point adsorption reflectometry and quartz crystal microgravimetry. Five different polyelectrolytescationic polyacrylamides of four charge densities and one cationic dextranwere examined. The adsorption kinetics was characterized using each technique, and the adsorption kinetics observed was in line with the impinging jet theory and the theory for one-dimensional diffusion, respectively. The polyelectrolyte adsorption increased with pH as an effect of the increased silica surface charge. A maximum in the saturation adsorption for both types of polyelectrolytes was found at 10 mM NaCl concentration. A significant adsorption also occurred at 1 M NaCl, which indicated a significant nonionic contribution to the adsorption mechanism. The fraction of solvent in the adsorbed layer was determined to be 70-80% by combining the two analysis techniques. This indicated a loose structure of the adsorbed layer and an extended conformation at the surface, favoring loops and tails. However, considering the solution structure with a hydrodynamic diameter larger than 100 nm for the CPAM and a thickness of the adsorbed layer on the order of 10 nm, the results showed that the adsorption is accompanied by a drastic change in polymer conformation. Furthermore, this conformation change takes place on a time scale far shorter than seconds.

Thin cellulose films were prepared by dissolving carboxymethylated cellulose fibers in N-methyl morpholine oxide and forming thin films on silicon wafers by spin-coating. The adsorption of cationic polyacrylamides and polydiallyldimethylammonium chloride onto these films was studied by stagnation point adsorption reflectometry (SPAR) and by quartz crystal microgravimetry with dissipation (QCM-D). The polyelectrolyte adsorption was studied by SPAR as a function of salt concentration, and it was found that the adsorption maximum was located at 1 mM NaCl for polyelectrolytes of low charge density and at 10 mM NaCl for polyelectrolytes of high charge density. Electrostatic screening led to complete elimination of the polyelectrolyte adsorption at salt concentrations of 300 mM NaCl. According to the QCM-D analysis, the cellulose films showed a pronounced swelling in water that took several hours to complete. Subsequent adsorption of polyelectrolytes onto the cellulose films led to a release of water from the cellulose, an effect that was substantial for polyelectrolytes of high charge density at low salt concentrations. The total mass change including water could therefore show either an increase or a decrease during adsorption onto the cellulose films, depending on the experimental conditions.

Hydrophobically modified and unmodified polyvinylamines (PVAm), including a total of five polymers, were tested against both gram-negative ( Escherichia coli ) and gram-positive ( Bacillus subtilis ) bacteria for antimicrobial activity. The assessment of PVAm in solution against bacteria is described, and the influence of the charge density and of the hydrophobic modification of the polyelectrolyte is discussed. The antimicrobial activity was found to depend upon the concentration of PVAm and also on the type of bacteria used. The results also indicated that no direct relationship exists between antimicrobial activity and charge density of the different PVAms. It was, however, observed that an alkyl chain length of six or eight alkane units had a substantial effect on the bacteria investigated. The best combined antibacterial activity for the two bacteria tested was achieved for PVAm with a C(6) alkane substituent (PVAm C(6)). To evaluate the antimicrobial activity on a solid substrate, PVAm C(6) was further studied after being deposited onto a glass slide and the results show a large reduction in bacterial infection.

Hyperbranched polymers (polyesteramides) were used as a cationic fixing agent to remove dissolved and colloidal substances (DCS) from the water phase in a fiber suspension. The relative turbidity, electrophoretic mobility, and average diameter of the colloidal particles were determined as a function of polyelectrolyte concentration. The results indicated that maximum removal of DCS was achieved at about zero electrophoretic mobility of the suspension where the negative surface charges of particles were neutralized by the oppositely charged hyperbranched polymer. The amount of hyperbranched polymers needed to maximize DCS fixation on the fibers was higher than the amount of poly-DADMAC (diallyldimethylammonium chloride) needed to reach the same effect. This was found to be due to the lower molecular weight and lower charge density of hyperbranched polymers. The lower molecular mass allowed penetration of these polymers into pores of fibers that resulted in higher polymer consumption before removal of the dissolved and colloidal substances from the fiber suspensions. A lower charge density further resulted in a higher saturation adsorption of the hyperbranched polymer. Experiments with both DCS and model-latex particles showed that the initial increase in relative turbidity was due to the aggregation of particles before fixation to fibers. The results from quartz crystal microbalance with dissipation (QCM-D) experiments showed that the efficiency of hyperbranched polymer and poly-DADMAC was similar even if they had different structure. Therefore, this study highlights the importance of molecular mass and charge density of the polymers as well as the surface structure of polymer layers which in turn gives implications for development of new structures of fixing agents.