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ABSTRACT Formation of alginate‐based interpenetrating networks and addition of nanoparticles into these gels are widely used strategies to enhance the mechanical properties of alginate gels used for delivery and biomedical applications. Our previous work demonstrated that alginate‐clay nanocomposite hydrogels containing poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) copolymers exhibited significant enhancement of elasticity and temperature‐dependent rheology. However, the behavior of PEO–PPO–PEO copolymers within an alginate network remains unclear. In this study, we use small‐angle neutron scattering (SANS) to investigate the interactions between the alginate network and PEO–PPO–PEO triblock chains. Our fitting results revealed that the triblock chains can form micelles integrated into the alginate gel “egg box” structure at higher temperatures. The presence of the alginate network influences the formation of PEO–PPO–PEO micelles in our gels, leading to elongated ellipsoidal micelles rather than spherical micelles. Interestingly, as the temperature increased, these micelles did not expand in all three dimensions, as observed for pure PEO–PPO–PEO solutions. Rather, the total size increased only in one direction while remaining the same in the other two directions, suggesting that the alginate networks restrict the growth of micelles. Furthermore, we did not observe the distinct higher‐order peaks that are typical of cubic PEO–PPO–PEO hydrogels; rather, relatively weak secondary peaks were observed. These results demonstrate that the presence of the alginate network significantly influences micelle formation and assembly in composite hydrogel systems. 

Colloidal clay Laponite forms a variety of arrested states that display interesting aging behavior. Microrheology has been applied to Laponite-based glasses and gels, but few studies evaluate the influence of probe particle size. In this work, we report the dynamics and microrheology of Laponite-polymer dispersions during aging using passive microrheology with three different probe particle sizes. At early aging times, the neat Laponite dispersion forms an arrested state; the nature of this state (e.g., a repulsive glass or gel) has remained the subject of debate. The addition of polymer retards gelation and melts the arrested state. While this melting has been observed at the macroscale and has been attributed to a re-entrant transition of a repulsive glass to a liquid state, to our knowledge, it has not been observed at the microscale. The delay of the gelation time needed to form an arrested state was found to depend on the polymer concentration and could vary from ∼24 h for neat Laponite to seven days for some Laponite-polymer samples. Significant effects of probe particle sizes are observed from the mean-squared displacement (MSD) curves as small and intermediate probe particles show diffusive motion, while the motion of large particles is restricted. By examining the factor of ⟨Δ r 2 (τ)⟩ a, structural heterogeneity can be confirmed through the strong size-dependence displayed. Different MSD trends of probe particles are obtained at longer aging times, but no significant changes occur after 30 days of aging. Our microrheology results also reveal significant effects of probe particle size.