Production of cellulose nanocrystals by hydrolysis in mixture of hydrochloric and nitric acids

Abstract

In this work, cellulose nanocrystals (CNC) have been produced by hydrothermal method in a mixture of hydrochloric and nitric acids in molar ratios of 8:2, 7:3, 6:4 and 5:5. Hydrolysis of sulphate cellulose in the mixtures of nitric and hydrochloric acids was conducted in a sealed thick-walled stainless steel vessel with a teflon insert for 3 h at 110 °S. Properties of CNC have been characterized by applying different methods: elemental analysis, thermogravimetric analysis, IR spectroscopy, polarization optical microscopy, scanning electron microscopy, and dynamic light scattering. Yield of CNC, size and charge of the CNC particles, degree of polymerization, tempera-ture of thermal destruction have been determined, and morphology of the CNC samples has been characterized. The highest CNC yield (32%) has been observed at a 7:3 ratio of nitric and hydro-chloric acids. It has been established that the CNC particles are spherical and have an average size of 60-80 nm. An assumption has been made that presence of a strong oxidant (nitric acid) may cause hydrolysis of both amorphous and crystalline (in part) regions of cellulose, which affects the final shape of the CNC particles. It has been shown that the hydrolysis in a mixture of nitric and hydrochloric acids causes an oxidation of primary hydroxyl groups of the cellulose pyranose ring and formation of surface carboxyl groups. The CNC aqueous suspensions demonstrate high col-loidal stability due to a rather high surface charge. It is noted that the CNC thermal stability is much higher than that of the CNC samples obtained by the standard sulfuric acid hydrolysis: the temperature of thermal destruction increases by 130-148 °S.