Polymorphic changes in cellulose nanofibers (CNFs) are closely related to their properties and applications, and it is of interest to investigate how polymorphic changes influence their properties. A comparative study on the properties of CNFs with cellulose I, I/II, and II polymorphs from wood was conducted herein. CNFs were obtained by chemical extraction combined with a simple and efficient mechanical treatment (one pass through a grinder). This process resulted in a relatively high yield of 80⁻85% after a simple grinding treatment. The polymorphic changes in the CNFs and the chemical composition, morphology, tensile performances, and thermal properties were systematically characterized and compared. The X-ray diffraction and FTIR analyses verified the existence of three types of purified pulps and CNFs with cellulose I, cellulose I/II, and cellulose II polymorphs (CNF-I, CNF-I/II, CNF-II). Morphological observations presented that these three types of CNFs all exhibited high aspect ratios and entangled structures. Tensile testing showed that the CNF films all exhibited high tensile strengths, and the fracture strains of the CNF-I/II (11.8%) and CNF-II (13.0%) films were noticeably increased compared to those of the CNF-I film (6.0%). If CNF-II is used as reinforcing material, its larger fracture strain can improve the mechanical performance of the CNF composites, such as fracture toughness and impact strength. In addition, CNF-I, CNF-I/II, and CNF-II films showed very low thermal expansion in the range 20⁻150 °C, with the coefficient of thermal expansion values of 9.4, 17.1, and 17.3 ppm/K, respectively. Thermogravimetric analysis (TGA) revealed that the degradation temperature of CNF-I and CNF-II was greater than that of CNF-I/II, which was likely due to increased α-cellulose content. This comparative study of the characterization of CNF-I, CNF-I/II, and CNF-II provides a theoretical basis for the application of CNFs with different polymorphs and could broaden the applications of CNFs.
Keywords: cellulose II; cellulose nanofibers; mechanical performance; polymorph; thermal property.