No Arabic abstract
By means of extensive simulations, we investigate concentrated solutions of globular single-chain nanoparticles (SCNPs), an emergent class of synthetic soft nano-objects. By increasing the concentration, the SCNPs show a reentrant behaviour in their structural and dynamical correlations, as well as a soft caging regime and weak dynamic heterogeneity. The latter is confirmed by validation of the Stokes-Einstein relation up to concentrations far beyond the overlap density. Therefore SCNPs arise as a new class of soft colloids, exhibiting slow dynamics and actualizing in a real system structural and dynamical anomalies proposed by models of ultrasoft particles. Quantitative differences in the dynamical behaviour depend on the SCNP deformability, which can be tuned through the degree of internal cross-linking.
We explore the origins of slow dynamics, aging and glassy rheology in soft and living matter. Non-diffusive slow dynamics and aging in materials characterised by crowding of the constituents can be explained in terms of structural rearrangement or remodelling events that occur within the jammed state. In this context, we introduce the jamming phase diagram proposed by Liu and Nagel to understand the ergodic-nonergodic transition in these systems, and discuss recent theoretical attempts to explain the unusual, faster-than-exponential dynamical structure factors observed in jammed soft materials. We next focus on the anomalous rheology (flow and deformation behaviour) ubiquitous in soft matter characterised by metastability and structural disorder, and refer to the Soft Glassy Rheology (SGR) model that quantifies the mechanical response of these systems and predicts aging under suitable conditions. As part of a survey of experimental work related to these issues, we present x-ray photon correlation spectroscopy (XPCS) results of the aging of laponite clay suspensions following rejuvenation. We conclude by exploring the scientific literature for recent theoretical advances in the understanding of these models and for experimental investigations aimed at testing their predictions.
In this article, we demonstrate a method for inducing reversible crystal-to-crystal transitions in binary mixtures of soft colloidal particles. Through a controlled decrease of salinity and increasingly dominating electrostatic interactions, a single sample is shown to reversibly organize into entropic crystals, electrostatic attraction-dominated crystals or aggregated gels, which we quantify using microscopy and image analysis. We furthermore analyze crystalline structures with bond order analysis to discern between two crystal phases. We observe the different phases using a sample holder geometry that allows both in situ salinity control and imaging through Confocal Laser Scanning Microscopy, and apply a synthesis method producing particles with high resolvability in microscopy with control over particle size. The particle softness provides for an enhanced crystallization speed, while altering the re-entrant melting behavior as compared to hard sphere systems. This work thus provides several tools for use in the reproducible manufacture and analysis of binary colloidal crystals.
Assemblies of purely repulsive and frictionless particles, such as emulsions or hard spheres, display very curious properties near their jamming transition, which occurs at the random close packing for mono-disperse spheres. Although such systems do not contain the long and cross-linked polymeric chains characterizing a rubber, they behave macroscopically in a similar way: the shear modulus $G$ can become infinitely smaller than the bulk modulus $B$. After reviewing recent theoretical results on the structure of such packing (in particular their coordination) I will propose an explanation for the observed scaling of the elastic moduli, and explain why the arguments both apply to soft and hard particles.
By employing monomer-resolved computer simulations and analytical considerations based on polymer scaling theory, we analyze the conformations and interactions of multiarm star polymers strongly adsorbed on a smooth, two-dimensional plane. We find a stronger stretching of the arms as well as a stronger repulsive, effective interaction than in the three dimensional case. In particular, the star size scales with the number of arms $f$ as $sim f^{1/4}$ and the effective interaction as $sim f^{2}$, as opposed to $sim f^{1/5}$ and $sim f^{3/2}$, respectively, in three dimensions. Our results demonstrate the dramatic effect that geometric confinement can have on the effective interactions and the subsequent correlations of soft colloids in general, for which the conformation can be altered as a result of geometrical constraints imposed on them.
Using Brownian dynamics simulations, we investigate the dynamics of colloids confined in two-dimensional narrow channels driven by a non-uniform force F(y). We considered linear-gradient, parabolic and delta-like driving-force profiles. This driving force induces melting of the colloidal solid (i.e., shear-induced melting), and the colloidal motion experiences a transition from elastic to plastic regime with increasing F. For intermediate F (i.e., in the transition region) the response of the system, i.e., the distribution of the velocities of the colloidal chains, in general does not coincide with the profile of the driving force F(y), and depends on the magnitude of F, the width of the channel and the density of colloids. For example, we show that the onset of plasticity is first observed near the boundaries while the motion in the central region is elastic. This is explained by: (i) (in)commensurability between the chains due to the larger density of colloids near the boundaries, and (ii) the gradient in F. Our study provides a deeper understanding of the dynamics of colloids in channels and could be accessed in experiments on colloids (or in dusty plasma) with, e.g., asymmetric channels or in the presence of a gradient potential field.