Mechanical Properties of Epoxy Networks with Metal Coordination Bonds: Insights from Temperature and Molar Mass Variation.

We investigate the thermal and mechanical properties of poly(ethylene glycol), PEG, networks with either solely covalent epoxy bonds (single networks, SNs) or coexisting epoxy and iron-catecholate bonds (dual networks, DNs). The latter has recently been shown to be a promising material that combines mechanical strength with significant deformability. Here, we address the previously unexplored effects of the temperature and PEG precursor molar mass on the mechanical properties of the networks.

Stress and flow inhomogeneity in shear-thickening suspensions.

Hypothesis: The viscosity of dense suspensions surges when the applied stress surpasses a material-specific critical threshold. There is growing evidence that the thickening transition involves non-uniform flow and stress with considerable spatiotemporal complexity. Nevertheless, it is anticipated that dense suspensions of calcium carbonate particles with purely repulsive interactions may not conform to this scenario, as indicated by local pressure measurements with millimeter spatial resolution.

Interpenetrated and Bridged Nanocylinders from Self-Assembled Star Block Copolymers.

The design of functional polymeric materials with tunable response requires a synergetic use of macromolecular architecture and interactions. Here, we combine experiments with computer simulations to demonstrate how physical properties of gels can be tailored at the molecular level, using star block copolymers with alternating block sequences as a paradigm. Telechelic star polymers containing attractive outer blocks self-assemble into soft patchy nanoparticles, whereas their mirror-image inverted architecture with inner attractive blocks yields micelles.

Yielding and resolidification of colloidal gels under constant stress.

We examine the macroscopic deformation of a colloidal depletion gel subjected to a step shear stress. Three regimes are identified depending on the magnitude of the applied stress: (i) for stresses below yield stress, the gel undergoes a weak creep in which the bulk deformation grows sublinearly with time similar to crystalline and amorphous solids. For stresses above yield stress, when the bulk deformation exceeds approximately the attraction range, the sublinear increase of deformation turns into a superlinear growth which signals the onset of non-linear rearrangements and yielding of the gel.

Self-Organization and Flow of Low-Functionality Telechelic Star Polymers with Varying Attraction.

We combine state-of-the art synthesis, simulations, and physical experiments to explore the tunable, responsive character of telechelic star polymers as models for soft patchy particles. We focus on the simplest possible system: a star comprising three asymmetric block copolymer arms with solvophilic inner and solvophobic outer blocks. Our dilute solution studies reveal the onset of a second slow mode in the intermediate scattering functions as the temperature decreases below the θ-point of the outer block, as well as the size reduction of single stars upon further decreasing temperature.

Residual stresses in colloidal gels.

A combination of experiments and Brownian Dynamics (BD) simulations is utilized to examine internal stresses in colloidal gels brought to rest from steady shear at different shear rates. A model colloidal gel with intermediate volume fraction is chosen where attractions between particles are introduced by adding non-adsorbing linear polymer chains. After flow cessation, the gel releases the stress in two distinct patterns: at high shear rates, where shear forces dominate over attractive forces, the shear-melted gel behaves as a liquid and releases stresses to zero after flow cessation.

Colloidal gels tuned by oscillatory shear.

We examine the microstructural and mechanical changes which occur during oscillatory shear flow and reformation after flow cessation of an intermediate volume fraction colloidal gel using rheometry and Brownian Dynamics (BD) simulations. A model depletion colloid-polymer mixture is used, comprising a hard sphere colloidal suspension with the addition of non-adsorbing linear polymer chains. The results reveal three distinct regimes depending on the strain amplitude of oscillatory shear.

Tuning colloidal gels by shear.

Using a powerful combination of experiments and simulations we demonstrate how the microstructure and its time evolution are linked with mechanical properties in a frustrated, out-of-equilibrium, particle gel under shear. An intermediate volume fraction colloid-polymer gel is used as a model system, allowing quantification of the interplay between interparticle attractions and shear forces. Rheometry, confocal microscopy and Brownian dynamics reveal that high shear rates, fully breaking the structure, lead after shear cessation to more homogeneous and stronger gels, whereas preshear at low rates creates largely heterogeneous weaker gels with reduced elasticity.

Controlling the kinetics of viscoelastic phase separation through self-assembly of spherical nanoparticles or block copolymers.

Viscoelastic phase separation (VPS) can produce a network structure of the minor phase, which needs to be stabilized for designing a heterogeneous structure with desired mechanical and electrical functions. In this work, we investigate the stabilization of the VPS-induced network structure in a dynamically asymmetric PS/PVME blend by incorporation of a SEBS-g-MA block copolymer or dimethyldichlorosilane modified nanosilica. The addition of SEBS-g-MA retards the volume shrinking process and slows down the kinetics of phase separation due to its localization at the PS/PVME interfaces.