Mixed-Acid-Assisted Hydrothermal Process for Simultaneous Preparation and Carboxylation of Needle-Shaped Cellulose Nanocrystals

In this study, a mixed-acid-assisted system utilizing a combination of a weak acid (citric acid, CA) and strong acid (H2SO4, SA) under hydrothermal reaction conditions was proposed for simultaneous preparation and modification (carboxylation) of cellulose nanocrystals (CNCs). Bleached bamboo pulp was used as the cellulose source, and the optimized reaction conditions were further used to produce carboxylated CNCs (cCNCs) from microcrystalline cellulose and Whatman 1 filter paper. Different concentrations of CA and SA (namely, 40 wt % CA (optimized concentration) and 5, 10, 20, and 30 wt % SA) were used for the hydrolytic processing of raw cellulosic material under hydrothermal conditions. The effect of various concentrations of CA and SA on the yield, carboxylate content, microstructure, crystallinity, thermal, and rheological characteristics of cCNCs were methodically investigated and contrasted. The optimized hydrothermal reaction conditions performed for 4 h at 100 °C using a mixture of 40 wt % CA and only 20 wt % SA yielded needle-shaped cCNCs with a yield higher than 70%. The carboxyl functionalization of CNCs was affirmed through Fourier transform infrared spectroscopy and conductometric titrimetric method. The results revealed the carboxylate content of 1.18 mmol/g corresponding to an average degree of oxidation of ∼0.20. The length of nanocrystals lies in the range of 280–420 nm with diameter ranging from 10 to 20 nm, as was perceived through microstructural analytical tools like field emission scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. Dynamic light scattering analysis gives an average size of ∼200 nm. The visual inspection revealed high colloidal stability of cCNCs dispersions, which was further supported through its appreciable Zeta potential value of ca. −49.5 mV. Further, the rheological characterizations revealed typical features reminiscent of critical gels showing elastic behavior of cCNCs. Nanocomposite films of hydroxypropyl methylcellulose (HPMC) with different loadings of cCNCs were fabricated using a simple solvent casting method. The incorporation of very small amounts of cCNCs (0.1 wt %) in HPMC resulted in ∼58% increment in tensile strength, ∼10% increment in modulus, and ∼82% increment in elongation. Moreover, the composite films exhibited high transparency and appreciable water barrier properties that allow their potential application as barrier and transparent films for various applications.