Green preparation of cellulose nanocrystals and nanofibers by ball milling assisted citric acid hydrolysis

In order to solve the drawbacks of carboxylated cellulose nanocrystals (CNCs) prepared by critic acid (CA) hydrolysis method, such as low yield and low esterification degree, herein, ball milling assisted CA hydrolysis method was applied to obtain carboxylated CNCs and cellulose nanofibers (CNFs) with fine and uniform size, high yield and carboxyl content, good crystallinity, and good thermal stability. It was discovered that the diameter of CNCs and CNFs were decreased and the size uniformity was improved. The yield of CNCs was obviously improved to 39.8 % due to the promoted esterification reaction, which was 3.3 times of that without ball milling. Moreover, the carboxyl group content of CNCs and CNFs were improved to a maximum of 0.52 and 0.48 mmol/g, respectively. As ball milling progressing, more amorphous regions were destroyed and cellulose bundles were dissociated, resulting in CNCs and CNFs with high crystallinity. The thermal decomposition temperature of CNCs and CNFs were ranged from 317 to 331℃, which was higher than that had reported. This work provided an effective route for carboxylated CNCs with good yield, esterification degree and other performance, which was beneficial for the subsequent applications in the field of biomaterials.