The interaction forces were investigated between matrix bitumen and four kinds of aggregates, including basalt, granite, limestone A, and limestone B in various pH solutions. The aim was to accurately evaluate the water damage resistance of bitumen mixtures at macroscopic and microscopic levels with a conjunctive method of boiling water tests, atomic force microscopy (AFM) colloidal probe technique, zeta potential measurements, and molecular dynamics simulation. Macroscopic evaluation was conducted through indoor water-boiled flaking rate tests to analyze the flaking rate and adhesion class of bitumen and aggregate. The microscopic forces were measured by AFM probe technique between bitumen and aggregate, zeta potential measurements were carried out and the extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was employed to interpret the bitumen–aggregate interaction behaviors. Molecular dynamics simulations were considered to explain the interface binding tendency between bitumen and aggregate. The AFM force measurements showed that the long-range repulsion forces changed to attractive forces and high adhesive forces with the pH change from 4 to 6. However, the strong long-range repulsive forces were decreased, compounded with a relative low adhesion in the alkaline solution. The long-range force between granite and bitumen was a strong attraction, and adhesion was strong when the solution pH was 4, which is a more special phenomenon. It may be due to the electrostatic attraction between the positive charge on the granite surface and the negative charge on the bitumen surface. Zeta potential values of bitumen droplets and aggregate particles exhibited an overall decreasing trend with increasing solution pH, and the variation of surface potential value is consistent with the variation trend of long-range force between aggregate and bitumen. The microscopic forces between bitumen and aggregate measured by AFM were validated by molecular dynamics simulations, revealing a strong correlation between debonding work and interfacial forces. The results indicate that the adhesion between aggregates and bitumen in aqueous solution followed the order: limestone A > limestone B > basalt > granite, and alkaline conditions are not conducive to preventing water damage in bitumen mixtures. It provides insights into the water stability mechanism of bitumen-aggregate at macroscopic and microscopic scales, offering theoretical support for preventing water damage in bitumen pavements.
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