Engineered cementitious composites containing polymeric fibers such as poly(vinyl alcohol) show high tensile ductility and toughness. The aim of the current study was to evaluate the effect of crystallinity degree of poly(vinyl alcohol) fibers on fiber debonding from cementitious matrix in the bending test. In this work, two types of poly(vinyl alcohol) fibers and one grade of polypropylene fiber were separately incorporated in cementitious composites. The chemical structure, surface chemistry, roughness, and microstructure of fibers were examined by Fourier transform infrared, attenuated total reflection, atomic force microscopy, and wide-angle X-ray diffraction tests, respectively. The compression and flexural behaviors of cementitious composites were also assessed. Attenuated total reflection results were indicative of similar surface chemistry for both poly(vinyl alcohol) fibers, while the main difference was observed in the case of degree of crystallinity, which plays an important role in the Poisson’s ratio. Finally, the way in which the degree of crystallinity and Poisson’s ratio of fibers can lead to premature debonding was described and confirmed by scanning electron microscopic images.
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