In this work we have investigated the effect of surface modification of fibres on the overall mechanical properties of high-density papers. Paper sheets were prepared by a combination of heat-pressing and polyelectrolyte Layer-by-Layer (LbL) modification of different softwood fibres. LbLs of Polyallylamine Hydrochloride (PAH) and Hyaluronic Acid (HA) were adsorbed onto unbleached kraft fibres and bleached Chemo-ThermoMechanical Pulp (CTMP) to improve the strength of the fibre–fibre joints in papers made from these fibres. Additionally, different sheet-making procedures were used to prepare a range of network densities with different degrees of fibre–fibre interaction in the system. The results demonstrate that interfacial adhesion within fibre–fibre joints plays a pivotal role in the network's performance, even at higher paper densities. Hygroexpansion measurements and fracture zone imaging with Scanning Electron Microscopy (SEM) further support the claim that stronger interactions between the fibres allow for a better utilisation of the inherent fibre properties. Surface treatments and network densification significantly improved the paper sheets' mechanical properties. Specifically, LbL-treatments alone increased specific stiffness up to 60% and specific strength by over 100%. This improvement is linked to the build-up of residual stresses during drying. Due to a high interaction between the fibres during water removal the fibres become constrained, leading to increased stretching of fibre segments. Strengthened fibre joints intensify this constraint, further increasing the stretch and, consequently, the paper's strength.
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