Polyelectrolyte Diffusion Into an Oppositely Charged Porous Substrate

Paper is a network material composed of a great number of fibers that interact with each other through fiber joints. In order to make a clear statement regarding observed changes being made in paper, it is vital to determine the structural level of paper that is being affected by chemical modifications. Polyelectrolytes having a wide range in molecular properties have been synthesized to investigate the adsorption behavior of cationic polyelectrolytes to cellulosic fibers. The interaction with the porous cell wall of cellulosic fibers is governed by the molecular properties of the polyelectrolyte. More specifically, polyelectrolytes having a low charge density are able to penetrate into the fiber cell wall, while high charge density polyelectrolytes are restricted to the exterior fiber surface. The molecular mass also influences the extent to which adsorption occurs within the cell wall, although this is typically only pronounced for low charge density polyelectrolytes. High charge density polyelectrolytes are generally restricted to the fiber surface due to strong Coulombic interactions between charged groups along the molecular backbone, which create a stiff molecular conformation. These results were confirmed by fluorescent labeling techniques, which allow the polyelectrolytes to be tracked inside the cell wall by confocal laser scanning microscopy. This approach was also used to demonstrate the effect of an electrolyte, which screens the Coulombic interactions and facilitates penetration into the cell wall. However, a considerable difference in the adsorption behavior of polyelectrolytes having similar molecular mass is still observed at high electrolyte concentration, where the electrostatic contributions are negligible. These differences are a consequence of a diffusion process that occurs on a longer times scale. Although polyelectrolyte adsorption to cellulosic fibers reaches a pseudo-equilibrium at short times, a driving force into the cell wall exists due to the bulk charge of the fiber. The time scale of this diffusion process depends on the polyelectrolyte properties, and was observed to persist for over 3 months. As the extent to which these polyelectrolytes penetrate into the cell wall has been ascertained, and the fibers can be crosslinked to different degrees in the cell wall or at the surface. Cationic acetal dextran was prepared as a model crosslinking agent, as the molecular mass, charge density and degree of acetal substitution can readily be controlled during synthesis. A considerable effect on the tensile properties and fracture toughness was observed for crosslinked paper, which could be attributed to either the fibers or the fiber joints. Crosslinking acted to stiffen the fibers and the fiber joints, which influenced the transfer of applied stresses through the paper structure. Changes in the material behavior at high relative humidity could be improved by crosslinking the fibers at the correct the structural level.