In this paper, the thermal effects on mechanical properties of polyvinyl alcohol fiber-reinforced engineered cementitious composites (PVA–ECC) were investigated systematically from perspective of multi-scales. At composite level, the compressive strength increases from 38 to 50 MPa as the samples were heated from 30 to 200 °C, whereas it declines to 20 MPa at 800 °C. In respect of tensile performance, at range of 30– 200 °C, the ultimate tensile stress and strain of ECC showed a decrease tendency with rising temperature, but still remained strain-hardening behavior at 200 °C. In addition, the elevated temperature exposures are adverse to multiple-cracking behavior of ECC. At micro-scale, it was found that the fiber/matrix interfacial bond reduces as exposure temperature rises, which is supposed to avail the fiber slippage, and thereby ductility of ECC. Nonetheless, through micromechanics-based analysis, the enhanced matrix toughness and severe deteriorated fiber strength prevailed over the above positive effect, which resulted in the decayed tensile properties of ECC.
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