Advances in nanotechnology have provided approaches for the fabrication of new composite materials for sensing. Flexible sensors can make up for the shortcomings of traditional strain sensors in monitoring the surface strain and cracks of concrete structures. Using reduced graphene oxide (RGO) as a conductive filler, cellulose nanofiber (CNF) as a dispersant and structural skeleton, and waterborne epoxy (WEP) as a polymer matrix, a flexible composite material with piezoresistive effect was prepared by the solution blending and solvent evaporation method. The mechanical, electrical, and electromechanical properties of the composite were investigated. The results show that CNF can significantly improve the dispersion of RGO in the WEP matrix and help to form stable reinforcing and conductive networks, leading to great changes in the mechanical properties and resistivity of the composite. The composite film can withstand large deformations (>55% strain), and the resistance change rate demonstrates a high sensitivity to mechanical strain with a gauge factor of 34–71. Within a 4% strain range, the piezoresistive property of the composite is stable with good linearity and repeatability. The performance of the flexible film sensor made of the composite is tested and it can monitor the strain and crack of the concrete surface well.
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