In situ generated cellulose nanoparticles to enhance the hydrophobicity of paper

Handsheets with in situ generated cellulose nanoparticles were made from oxidized pulp fibers prepared by 2,2,6,6-tetramethylpiperidinyl-1-oxyl-mediated oxidation of kraft fiber with sodium hypochlorite and sodium bromide. The oxidized pulp fibers were blended prior to handsheet formation for short times (1–3 min). From gravimetric analysis of the supernatant, yield of cellulose nanoparticles generated from this blending process were up to 9.5 dry wt%. Scanning electron microscopy showed that the handsheets fabricated in a wetlay process had increased smoothness with increased blending time. A significant decrease in water vapor transmission rate for the sheets supported the hypothesis that cellulose nanoparticles fill the empty spaces between pulp fibers throughout the handsheet affording a more dense structure. Oxidation significantly enhanced the tensile index of the handsheets and this value was further improved by blending for 2 min. The handsheets were treated with a solution of octadecylamine (ODA) modifying the surface chemistry of the paper. Irreversibly adsorbed ODA on the oxidized cellulose surfaces after extensive extraction was confirmed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Sessile drop contact angle tests for modified handsheets illustrated its enhanced hydrophobicity with contact angles over 90°. Overall the study developed a novel route to make paper with enhanced functionality without the need to separately deposit nanocellulose onto the paper surface.