Microstructural Reconstruction and Interfacial Regulation in a CaCl2–Sodium Polyacrylate Organic–Inorganic Composite System for High-Liquid-Limit Clay

High-liquid-limit clay exhibits pronounced water sensitivity due to the strong electrostatic repulsion and weak interparticle bonding within its microstructure, which often limits its direct engineering uses and complicates the reuse of excavated clayey soils generated during the construction of transportation infrastructure. In this study, inorganic salts (KCl, CaCl2 and FeCl3) and carboxyl-containing polymers (PAAS, HPMA and CMC) were screened to construct organic–inorganic composite stabilization systems. Based on the screening results, an organic–inorganic composite system composed of CaCl2 and sodium polyacrylate (PAAS) was developed to regulate interfacial interactions and induce microstructural reconstruction in clay. The synergistic mechanisms governing particle aggregation and dispersion were systematically investigated through Atterberg limit tests, zeta potential measurements, DLVO theoretical calculations, particle size analysis, scanning electron microscopy (SEM) and immersion disintegration experiments, combined with multivariate statistical modeling. Among the tested salt–polymer formulations, a composite system with 2% CaCl2 and 0.1% PAAS showed the most favorable overall performance, achieving an optimal balance between electrostatic compression and steric stabilization, leading to enhanced structural integrity and delayed water-induced disintegration. Ca2+ ions compress the diffuse double layer and promote particle flocculation, whereas adsorbed PAAS chains introduce steric hindrance and interfacial modification. Their synergistic interaction reconstructs the pore–aggregate framework and regulates the interparticle potential energy landscape. DLVO analysis indicates that the optimized system attains a moderate critical interaction distance (hc = 7.31 nm) and primary minimum depth (DPM = −2.72 × 10−16 J), reflecting a balanced interfacial bonding state. Multivariate statistical analyses further reveal a dual control pathway, in which consistency primarily governs disintegration duration, with additional contributions from surface electrochemical properties, while surface properties, soil structure and consistency collectively influence disintegration initiation. These findings elucidate the interfacial regulation and structural evolution mechanisms in organic–inorganic composite systems and provide insights into the design of composite modifiers for water-sensitive particulate materials, particularly for the resource reuse of high-liquid-limit clay excavated during the construction of transportation infrastructure and related geotechnical engineering applications.