Physical Chemistry of Conductive Core–Shell Superabsorbent Polymers: Mechanisms, Interfacial Phenomena, and Implications for Construction Materials

Conductive core–shell superabsorbent polymers (SAPs) are emerging as multifunctional additives for cementitious materials, combining moisture management with electrical functionality. In cement-based systems, a swellable polymeric core enables internal curing and crack-sealing through controlled water uptake and release, while a conductive shell introduces ionic and/or electronic charge transport, addressing key limitations of conventional non-conductive SAPs. This dual functionality provides a pathway toward smart cementitious composites with enhanced durability, self-sensing capability, and moisture-responsive behavior. This review focuses on the physical chemistry mechanisms governing conductive core–shell SAPs in cementitious environments, with emphasis on swelling thermodynamics, water transport kinetics, interfacial phenomena, and charge transport mechanisms. The roles of osmotic pressure, elastic network constraints, ionic effects, and pore solution chemistry are critically discussed, together with their impact on conductivity, hydration processes, microstructure development, and long-term performance. The relative contributions of ionic and electronic conduction are examined in relation to hydration state, shell morphology, and percolation of conductive networks. In addition, the relevance of core–shell SAP architectures to sustainable packaging is briefly discussed as a secondary application, illustrating how similar physicochemical principles—such as moisture buffering and functional coatings—apply beyond construction materials. Finally, key knowledge gaps are identified, including long-term stability in highly alkaline environments, trade-offs between swelling capacity and conductivity, environmental impacts of conductive phases, and the need for integrated experimental and modeling approaches. Addressing these challenges is essential for the rational design and practical implementation of conductive core–shell SAPs in next-generation cementitious materials.