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The brittle nature of concrete limits the further development, while the addition of polymer can enhance the toughness and improve the working performance. Understanding the mechanical properties and failure mode of polyurethane cement composites (PUCC) is of great significance in the field of construction engineering. To solve these issues, in this paper, the tensile and compressive properties are studied. The tensile/compressive strength, elastic modulus, toughness, strain capacity and the failure mechanism were analyzed. The results showed that compared with the reference group (RF), the compressive strength of PUCC was decreased by 33%. However, rubber powder could enhance the toughness of samples up to 1.19 times than RF. Polyethylene fiber was hard to disperse because of the poor fluidity of the matrix, therefore, the mechanical properties of PUCC did not change obviously. But due to the bridging effect of fiber, the failure mode was relative intact. Not only the irregular shape of basalt would decrease the interfacial adhesion, but also the polyurethane has weakened the cohesion. The mechanical properties of concrete were reduced because of the formation of interfacial transition zone between basalt and cement matrix. Therefore, the tensile and compressive strength was decreased by 19.7% and 11.8%, respectively. Moreover, the incorporation of basalt shortens the deformation time and intensifies the failure degree of the specimen. Moreover, this study takes a three-stage model to describe the compressive stress–strain behavior of PUCC. There is a good correlation between the constitutive model and the experimental results, and the simulation is accurate.
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