Alkali-activation of cellulose nanofibrils to facilitate surface chemical modification under aqueous conditions

In this study, we developed a surface-activation technique for cellulose nanofibrils (CNFs) using mild-alkali and aqueous conditions. CNFs were initially processed using the aqueous counter collision (ACC) method to produce Janus-type amphiphilic CNFs with both hydrophilic and hydrophobic faces on the surface of a single nanofibril (ACC-CNF). Selective functionalization of the hydroxy groups on the hydrophilic faces creates an opportunity to develop novel nano-building blocks that introduce heterogeneous and tailored surface characteristics into the design of nanomaterials. In this study, alkaline conditions were used to activate the hydroxy groups on the surface of ACC-CNFs as a pre-treatment for the partial crystalline transformation from cellulose I to cellulose II. We found that alkali treatment with sodium hydroxide (NaOH) solutions (concentration range 1–7 wt%) did not fully transform the structure of ACC-CNFs into cellulose II, nor change the morphology of nanofibrils, as seen from their wide-angle X-ray diffraction patterns and atomic force microscopy images. We also found that the hydroxy groups at the surface region of the ACC-CNFs were sufficiently reactive under the moderate alkali and aqueous conditions to undergo subsequent carboxymethylation. Therefore, alkali treatment of ACC-CNFs with a 1–7 wt% NaOH solution rendered the surface of the ACC-CNFs as sufficiently reactive for chemical modification without morphological changes. This simple method for surface activation of CNFs can be useful in the development of future sustainable and novel materials for a variety of applications.