Structure and rheological studies of phosphorylated cellulose nanofibrils suspensions

Cellulose nanofibrils (CNFs) are normally handled in the form of aqueous suspensions. Therefore, their rheology and intrinsic flow features in an aqueous state also fascinated the researchers. However, understanding the structure-rheology relationship remains a profound challenge to design CNFs with desirable properties. For that purpose, jute fibers were used as source material (Corchorus olitorius) to produce CNFs, and pretreatment using phosphorylation was applied to facilitate the fibrillation during ultra-sonication. This study aims to investigate the relationship between the microstructure and their rheology for CNF aqueous suspensions as influenced by the temperature and concentration of CNF. The surface chemistry, fiber diameter distribution, crystalline structure, thermal stability, and rheological properties of the obtained CNFs were characterized and compared. The grafting of phosphorous moieties on the surface of the fibers was confirmed by the FTIR, XPS analyses, elemental analyses, and zeta potential. Despite influencing crystallinity, phosphorylation enhanced the diameter of nanofibers. The results demonstrated that phosphorylation did not alter the main chemical structure of cellulose. The crystallographic form of the obtained CNFs remained cellulose I. The resulting fibers have nanometric dimensions (<100 nm) with high absolute zeta potential values (>30 mV). A substantial improvement in flame retardancy has also been noted for CNF due to the presence of phosphate groups. Both steady-state and dynamic rheological measurements were improved significantly upon increasing concentration from 0.5 to 2.5 wt%. All the CNF suspensions demonstrated typical shear-thinning behavior and gel-like viscoelastic character even at low concertation (0.5 wt%) due to the construction of a wire-like matrix structure. The frequency and temperature alteration, however, do not affect the viscoelastic gel-like properties of the CNF suspensions.