Real-time measurements of crystallization processes in viscoelastic polymeric photonic crystals.

Abstract

We present a study of the dynamic shear ordering of viscoelastic photonic crystals, based on core-shell polymeric composite particles. Using an adapted shear-cell arrangement, the crystalline ordering of the material under conditions of oscillatory shear is interrogated in real time, through both video imaging and from the optical transmission spectra of the cell. In order to gain a deeper understanding of the macroscopic influences of shear on the crystallization process in this solvent-free system, the development of bulk ordering is studied as a function of the key parameters including duty cycle and shear-strain magnitude. In particular, optimal ordering is observed from a prerandomized sample at shear strains of around 160%, for 1-Hz oscillations. This ordering reaches completion over time scales of order 10 s. These observations suggest significant local strains are needed to drive nanoparticles through energy barriers, and that local creep is needed to break temporal symmetry in such high-viscosity nanoassemblies. Crystal shear-melting effects are also characterized under conditions of constant shear rate. These quantitative experiments aim to stimulate the development of theoretical models which can deal with the strong local particle interactions in this system.