Reinforcement Behavior of Chemically Unmodified Cellulose Nanofiber in Natural Rubber Nanocomposites

We investigated the reinforcement behavior of small amounts of chemically unmodified cellulose nanofiber (CNF) in eco-friendly natural rubber (NR) nanocomposites. For this purpose, NR nanocomposites filled with 1, 3, and 5 parts per hundred rubber (phr) of cellulose nanofiber (CNF) were prepared by a latex mixing method. By using TEM, a tensile test, DMA, WAXD, a bound rubber test, and gel content measurements, the effect of CNF concentration on the structure–property relationship and reinforcing mechanism of the CNF/NR nanocomposite was revealed. Increasing the content of CNF resulted in decreased dispersibility of the nanofiber in the NR matrix. It was found that the stress upturn in the stress–strain curves was remarkably enhanced when the NR was combined with 1–3 phr CNF, and a noticeable increase in tensile strength (an approximately 122% increase in tensile strength over that of NR) was observed without sacrificing the flexibility of the NR in the NR filled with 1 phr CNF, though no acceleration in their strain-induced crystallization was observed. Since the NR chains were not inserted in the uniformly dispersed CNF bundles, the reinforcement behavior by the small content of CNF might be attributed to the shear stress transfer at the CNF/NR interface through the interfacial interaction (i.e., physical entanglement) between the nano-dispersed CNFs and the NR chains. However, at a higher CNF filling content (5 phr), the CNFs formed micron-sized aggregates in the NR matrix, which significantly induced the local stress concentration and promoted strain-induced crystallization, causing a substantially increased modulus but reduced the strain at the rupture of the NR.