To explore the influence of the polyurethane blending ratio on the micro-characteristics of polyurethane-modified asphalt, three samples of the modified asphalt with different blending ratios (40%, 50%, and 60%) were prepared. Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), and scanning electron microscopy (SEM) were employed to elucidate the modification mechanism of polyurethane-modified asphalt. To investigate how the preparation method affects the performance of polyurethane-modified asphalt mixtures, two different preparation methods, namely internal blending and external blending, were adopted. The road performance of the polyurethane-modified asphalt mixtures was evaluated through the utilization of rutting tests, low-temperature trabecular bending tests, and freeze–thaw splitting tests. The FTIR test results indicate that during the modification of polyurethane, there is a change in both the intensity and position of the absorption peak, which affects the local arrangement of the molecular structure. Upon reaching a polyurethane blending ratio of 50%, a cross-linked network structure that is similar to polyurethane is formed. The results of the AFM test demonstrate that an increase in polyurethane content results in a corresponding increase in surface roughness. At a polyurethane content of 50%, the curing reaction is most effective, which is beneficial for enhancing the bonding performance between the asphalt and the aggregate, thereby enhancing the overall water stability of the mixture. The results of the scanning electron microscopy (SEM) tests indicate that the microstructure is more stable when the polyurethane content is 50%. The results of the performance test of the polyurethane-modified asphalt mixture indicate that the dynamic stability of the polyurethane-modified asphalt mixture is approximately four times that of the SBS-modified asphalt mixture. The flexural tensile strength and maximum flexural strain of the polyurethane-modified asphalt mixture are, respectively, 1.5 and 3.2 times those of the SBS-modified asphalt mixture, indicating that its anti-deformation ability is stronger in a low-temperature environment, and it is found that the low-temperature performance of the mixture prepared with the internal blending method is better than that with the external blending method. The splitting strength of the polyurethane asphalt mixture before and after freezing and thawing is greater than that of an SBS asphalt mixture: before freezing and thawing, by about 3.8 times; after freezing and thawing, by about 3 times. Although the freezing and thawing of the polyurethane mixture has damage, it still meets the requirements of the use of pavement materials. It can be observed that the incorporation of polyurethane alters the internal structure of the asphalt, which markedly enhances the properties of the asphalt mixture and offers a novel perspective on the development of modified asphalt materials.
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