Interplay of electrolyte concentration and molecular weight of polyDADMAC on cellulose surface adsorption

Cationic polyelectrolytes (PEs) are commonly used additives in manufacturing of cellulose based products such as regenerated fibers and paper to tailor their product properties. Here we are studying the adsorption of poly(diallyldimethylammonium chloride), PD, on cellulose, using in situ surface plasmon resonance spectroscopy (SPR) measurements. We employ model surfaces from regenerated cellulose xanthate (CX) and trimethylsilyl cellulose (TMSC), mimicking industrially relevant regenerated cellulose substrates. The effects of the PDs molecular weight were strongly depending on the ionic strength and type of electrolyte (NaCl vs CaCl₂). Without electrolytes, the adsorption was monolayer-type, i.e. independent of molecular weight. At moderate ionic strength, adsorption increased due to more pronounced PE coiling, while at high ionic strength electrostatic shielding strongly reduced adsorption of PDs. Results exhibited pronounced differences for the chosen substrates (cellulose regenerated from xanthate (CX_reg) vs. regenerated from trimethylsilyl cellulose, TMSC_reg). Consistently higher adsorbed amounts of the PD were determined on CX_reg surfaces compared TMSC. This can be attributed to a more negative zeta potential, a higher AFM roughness and a higher degree of swelling (investigated by QCM-D) of the CX_reg substrates.