Soft glassy colloidal arrays in an ionic liquid: colloidal glass transition, ionic transport, and structural color in relation to microstructure

J Phys Chem B. 2010 Oct 21;114(41):13095-103. doi: 10.1021/jp106872w.

Abstract

The colloidal glass transition, ionic transport, and optical properties of soft glassy colloidal arrays (SGCAs) that consist of poly(methyl methacrylate) (PMMA)-grafted silica nanoparticles (PMMA-g-NPs) and a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)amide ([C(2)mim][NTf(2)]), were investigated. At lower particle concentrations, PMMA-g-NPs were well-suspended in the IL without any aggregation or sedimentation, and the dilute suspensions showed liquid-like behavior. However, above a certain particle concentration, the suspensions became solidified and exhibited different structural colors depending on the particle concentrations. The liquid-solid transition of the SGCAs was essentially caused by colloidal glass transition. Due to the soft repulsive interaction between the particles, the effective volume fraction of the particle (ϕ(eff)) required for colloidal glass transition was higher than that of the hard sphere system and found to be approximately 0.70-0.74. The SGCA had sufficient ionic conductivity, which was greater than 10(-3) S cm(-1) at room temperature, even in the highly concentrated region. For ionic transport of the cation and the anion in the SGCAs, the decrease in diffusivity observed with the addition of the particles (D(g)/D(0)) was slightly greater for the [NTf(2)] anion than that of the [C(2)mim] cation, suggesting that the [NTf(2)] anion preferentially interacts with the PMMA chains. The SGCAs showed homogeneous, nonbrilliant, and angle-independent structural colors above the glass transition volume fraction. In addition, the color of the SGCAs changed from red to green to blue as the particle concentration increased. A linear relationship was found between the maximum wavelength of the reflection spectra and the center-to-center distance in the SGCAs.