Viscoelasticity of colloidal polycrystals doped with impurities.

We investigate how the microstructure of a colloidal polycrystal influences its linear visco-elasticity. We use thermosensitive copolymer micelles that arrange in water in a cubic crystalline lattice, yielding a colloidal polycrystal. The polycrystal is doped with a small amount of nanoparticles, of size comparable to that of the micelles, which behave as impurities and thus partially segregate in the grain boundaries. We show that the shear elastic modulus only depends on the packing of the micelles and varies neither with the presence of nanoparticles nor with the crystal microstructure. By contrast, we find that the loss modulus is strongly affected by the presence of nanoparticles. A comparison between rheology data and small-angle neutron-scattering data suggests that the loss modulus is dictated by the total amount of nanoparticles in the grain boundaries, which in turn depends on the sample microstructure.

Correlation between crystalline order and vitrification in colloidal monolayers.

We investigate experimentally the relationship between local structure and dynamical arrest in a quasi-2d colloidal model system which approximates hard discs. We introduce polydispersity to the system to suppress crystallisation. Upon compression, the increase in structural relaxation time is accompanied by the emergence of local hexagonal symmetry. Examining the dynamical heterogeneity of the system, we identify three types of motion: 'zero-dimensional' corresponding to ß-relaxation, 'one-dimensional' or stringlike motion and '2D' motion. The dynamic heterogeneity is correlated with the local order, that is to say locally hexagonal regions are more likely to be dynamically slow. However, we find that lengthscales corresponding to dynamic heterogeneity and local structure do not appear to scale together approaching the glass transition.

Plasticity of a colloidal polycrystal under cyclic shear.

We use confocal microscopy and time-resolved light scattering to investigate plasticity in a colloidal polycrystal, following the evolution of the network of grain boundaries as the sample is submitted to thousands of shear deformation cycles. The grain boundary motion is found to be ballistic, with a velocity distribution function exhibiting nontrivial power law tails. The shear-induced dynamics initially slow down, similarly to the aging of the spontaneous dynamics in glassy materials, but eventually reach a steady state. Surprisingly, the crossover time between the initial aging regime and the steady state decreases with increasing probed length scale, hinting at a hierarchical organization of the grain boundary dynamics.

Structure of nanoparticles embedded in micellar polycrystals.

We investigate by scattering techniques the structure of water-based soft composite materials comprising a crystal made of Pluronic block-copolymer micelles arranged in a face-centered cubic lattice and a small amount (at most 2% by volume) of silica nanoparticles, of size comparable to that of the micelles. The copolymer is thermosensitive: it is hydrophilic and fully dissolved in water at low temperature (T ~ 0 °C), and self-assembles into micelles at room temperature, where the block-copolymer is amphiphilic. We use contrast matching small-angle neuron scattering experiments to independently probe the structure of the nanoparticles and that of the polymer. We find that the nanoparticles do not perturb the crystalline order. In addition, a structure peak is measured for the silica nanoparticles dispersed in the polycrystalline samples. This implies that the samples are spatially heterogeneous and comprise, without macroscopic phase separation, silica-poor and silica-rich regions. We show that the nanoparticle concentration in the silica-rich regions is about 10-fold the average concentration. These regions are grain boundaries between crystallites, where nanoparticles concentrate, as shown by static light scattering and by light microscopy imaging of the samples. We show that the temperature rate at which the sample is prepared strongly influence the segregation of the nanoparticles in the grain-boundaries.