Recycled paper and some hardwood paper often display poorer mechanical properties, which hinder its practical applications and need to be addressed. In this work, cellulose nanofibrils (CNFs) obtained by a combined process of enzymatic hydrolysis and grinding (EG-CNFs), grinding and microfluidization (GH-CNFs) or TEMPO-mediated oxidation and grinding (TE-CNFs) were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Moreover, CNFs were made into films on which some characterizations including X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and UV–Vis transmittance spectroscopy were implemented. Results showed that CNF fibrillation was promoted as times of passes increased in microfluidization, and CNFs pretreated by enzyme possessed shorter length. Crystallinity of CNFs was related to CNF manufacturing methods, while CNF films’ transparency was correlated to CNF diameter distributions. Moreover, CNFs were applied with different dosages on recycled and hardwood paper. Lengths of CNFs, strength of CNF network, and pulp properties were critical factors affecting the mechanical strength of CNFs-enhanced paper. GH-CNFs showed better strengthened effect on tensile strength of paper than TE-CNFs and EG-CNFs. The best overall improvement was achieved at GH-CNF10 dosage of 5.0 wt% on hardwood paper. The increment of tensile index, burst index, and folding endurance were 108.32%, 104.65%, and 600%, respectively. This work aims to find out the relationship between production methods and morphologies of CNFs and how the morphological characteristics of CNFs affecting the mechanical performance of paper when they are added as strength additives.
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