Solvent Wrapped Metastable Colloidal Crystals: Highly Mutable Colloidal Assemblies Sensitive to Weak External Disturbance

Solvent wrapped “metastable” crystalline colloidal arrays (CCAs) have been prepared by supersaturation induced precipitation and self-assembly of monodisperse particles in polar/nonpolar organic solvents. These metastable CCAs possess ordered structures but with less stability comparing with traditionally fixed colloidal crystal systems. They are stabilized by the balance between long-range attraction and electrostatic repulsion of neighboring like-charged particles. Monitoring the reflection intensity during evaporation suggests that these crystals can exist for several hours at 90 °C and even longer at room temperature. Based on the evolution of particle volume fraction in whole suspension (ϕ_SiO₂), crystal phase (ϕ_crystal), and liquid phase (ϕ_liquid), the formation of metastable CCAs can be understood as a microscopic phase separation process, where the homogeneous dispersion will separate into a “crystal phase” with orderly stacked particles and a “liquid phase” with randomly dispersed particles. Further calculation of the volume fraction of crystal phase (<i>V</i>_crystal/<i>V</i>_total) and the ratio of particles in crystal phase (<i>f</i>_crystal) shows that with the increase of designed Φ_SiO₂, more particles precipitate to form colloidal crystals with larger sizes but the lattice spacing of the microcrystals remains constant. Unlike fixed or traditional responsive CCAs, these metastable CCAs can reversibly assemble and disassemble with great ease, because little energy is involved or required in this transformation. Therefore, they can sense weak external disturbances, including subtle motion and slight friction or shearing forces