Extended Wertheim theory predicts the anomalous chain length distributions of divalent patchy particles under extreme confinement

Colloidal patchy particles with divalent attractive interaction can self-assemble into linear polymer chains. Their equilibrium properties in 2D and 3D are well described by Wertheim's thermodynamic perturbation theory which predicts a well-defined exponentially decaying equilibrium chain length distribution. In experimental realizations, due to gravity, particles sediment to the bottom of the suspension forming a monolayer of particles with a gravitational height smaller than the particle diameter. In accordance with experiments, an anomalously high monomer concentration is observed in simulations which is not well understood. To account for this observation, we interpret the polymerization as taking place in a highly confined quasi-2D plane and extend the Wertheim thermodynamic perturbation theory by defining addition reactions constants as functions of the chain length. We derive the theory, test it on simple square well potentials, and apply it to the experimental case of synthetic colloidal patchy particles immersed in a binary liquid mixture that are described by an accurate effective critical Casimir patchy particle potential. The important interaction parameters entering the theory are explicitly computed using the integral method in combination with Monte Carlo sampling. Without any adjustable parameter, the predictions of the chain length distribution are in excellent agreement with explicit simulations of self-assembling particles. We discuss generality of the approach, and its application range.Comment: The following article has been submitted to The Journal of Chemical Physic

Shear-induced anisotropic decay of correlations in hard-sphere colloidal glasses

Spatial correlations of microscopic fluctuations are investigated via real-space experiments and computer simulations of colloidal glasses under steady shear. It is shown that while the distribution of one-particle fluctuations is always isotropic regardless of the relative importance of shear as compared to thermal fluctuations, their spatial correlations show a marked sensitivity to the competition between shear-induced and thermally activated relaxation. Correlations are isotropic in the thermally dominated regime, but develop strong anisotropy as shear dominates the dynamics of microscopic fluctuations. We discuss the relevance of this observation for a better understanding of flow heterogeneity in sheared amorphous solids.Comment: 6 pages, 4 figure

Yielding and irreversible deformation below the microscale: Surface effects and non-mean-field plastic avalanches

Nanoindentation techniques recently developed to measure the mechanical response of crystals under external loading conditions reveal new phenomena upon decreasing sample size below the microscale. At small length scales, material resistance to irreversible deformation depends on sample morphology. Here we study the mechanisms of yield and plastic flow in inherently small crystals under uniaxial compression. Discrete structural rearrangements emerge as series of abrupt discontinuities in stress-strain curves. We obtain the theoretical dependence of the yield stress on system size and geometry and elucidate the statistical properties of plastic deformation at such scales. Our results show that the absence of dislocation storage leads to crucial effects on the statistics of plastic events, ultimately affecting the universal scaling behavior observed at larger scales.Comment: Supporting Videos available at http://dx.plos.org/10.1371/journal.pone.002041

Colloidal aggregation in microgravity by critical Casimir forces

By using the critical Casimir force, we study the attractive strength dependent aggregation of colloids with and without gravity by means of Near Field scattering. Significant differences were seen between microgravity and ground experiments, both in the structure of the formed fractal aggregates as well as the kinetics of growth. Ground measurements are severely affected by sedimentation resulting in reaction limited behavior. In microgravity, a purely diffusive behavior is seen reflected both in the measured fractal dimensions for the aggregates as well as the power law behavior in the rate of growth. Formed aggregates become more open as the attractive strength increases.Comment: 4 pages, 3 figure