Viscoelastic interfacial structures in undersaturated calcium solutions under nanoconfinement

Abstract: Calcium mineralisation underpins processes ranging from biomineralisation to scalable carbon storage, yet the earliest stages of nucleation remain unresolved. Here we investigate calcium-containing solutions under nanoscopic confinement while remaining undersaturated with respect to bulk calcium carbonate precipitation. Using sensitive surface force measurements, we identify a long-range non-DLVO repulsive interaction specific to calcium solutions, which we attribute to hydrated ion networks at mineral interfaces. These interfacial networks exhibit viscoelastic behaviour distinct from the bulk solution, persist across a broad pH range, and can be disrupted by competing ions with strong surface affinity. Our findings provide experimental evidence that stable hydrated ion networks can emerge at mineral interfaces under undersaturated conditions, supporting the possibility that interfaces and confinement stabilise intermediate ion assemblies prior to nucleation. These results bridge classical and nonclassical descriptions of mineral nucleation and highlight the central role of interfaces and confinement in directing crystallisation pathways.