Interaction Mechanism of Anionic Lignin and Cationic Soft Surface in Saline Systems

Lignin has a complicated three-dimensional structure that is different from other synthetic and bio-based materials. In this work, we first examined the physicochemical behavior, i.e., apparent hydrodynamic radius (R_h) and ζ-potential, of carboxymethylated lignin (CM) in a saline system. Then, the detailed interaction and adsorption behavior of CM on a cationic poly(diallyldimethylammonium chloride) (PDADMAC)-coated surface were investigated in a saline system by a quartz crystal microbalance with dissipation. The theoretical and experimental adsorption data revealed that CM made limited surface coverage at a low salt concentration via charge neutralization following an intrinsic compensation mechanism. At a higher salt concentration, the adsorption of CM was improved significantly following the extrinsic compensation mechanism and nonionic interaction (e.g., hydrophobic interaction). The adsorption affinity of CM in the urea environment revealed the contribution (10-30%) of hydrogen bonding in the adsorption of CM on the PDADMAC surface. Contrary to what was found for the CM, the adsorption of a linear poly(acrylic acid-acrylamide) (PAM) on the PDADMAC surface exhibited a dramatic decrease at higher salinity, possibly due to the absence of nonionic and hydrophobic interactions between PAM and the surface. The findings of this study showed the superior adsorption performance of the lignin-based polyelectrolytes to the synthetic ones in salt-containing systems.