Real-time measurements of crystallization processes in visco-elastic polymeric photonic crystals

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.This work is supported by EPSRC Grants No. EP/G060649/1, No. EP/E040241, and No. EP/H027130/1, and ERC Grant No. LINASS 32050

Large-scale ordering of nanoparticles using viscoelastic shear processing

This is the author accepted manuscript. It is currently under an indefinite embargo pending publication by Nature Publishing Group.Despite the availability of elaborate varieties of nanoparticles, their assembly into regular superstructures and photonic materials remains challenging. Here we show how flexible films of stacked polymer nanoparticles can be directly assembled in a roll-to-roll process using a bending-induced oscillatory shear (BIOS) technique. For sub-micron spherical nanoparticles, this gives elastomeric photonic crystals termed polymer opals showing extremely strong structural colour. With oscillatory strain amplitudes of 300%, crystallisation initiates at the wall and develops quickly across the bulk within only 5 oscillations yielding sharp intense reflectance peaks of tunable colour. The resulting structure of randomly stacked hexagonal close-packed layers parallel to the shear plane, is improved by shearing bidirectionally, alternating between two in-plane directions. Our theoretical framework indicates how the reduction in shear viscosity with increasing order of each layer accounts for these results, even when diffusion is totally absent. This general principle of shear ordering in viscoelastic media opens the way to manufacturable photonics materials, and forms a generic tool for ordering nanoparticles.We acknowledge EPSRC grants EP/G060649/1, EP/H027130/1, EP/E040241, EP/L027151/1 and EU ERC grants LINASS 320503 and FP7 291522-3DIMAGE