Overshoots in stress strain curves: Colloid experiments and schematic mode coupling theory

The stress versus strain curves in dense colloidal dispersions under start-up shear flow are investigated combining experiments on model core-shell microgels, computer simulations of hard disk mixtures, and mode coupling theory. In dense fluid and glassy states, the transient stresses exhibit first a linear increase with the accumulated strain, then a maximum ('stress overshoot') for strain values around 5%, before finally approaching the stationary value, which makes up the flow curve. These phenomena arise in well-equilibrated systems and for homogeneous flows, indicating that they are generic phenomena of the shear-driven transient structural relaxation. Microscopic mode coupling theory (generalized to flowing states by integration through the transients) derives them from the transient stress correlations, which first exhibit a plateau (corresponding to the solid-like elastic shear modulus) at intermediate times, and then negative stress correlations during the final decay. We introduce and validate a schematic model within mode coupling theory which captures all of these phenomena and handily can be used to jointly analyse linear and large-amplitude moduli, flow curves, and stress-strain curves. This is done by introducing a new strain- and time-dependent vertex into the relation between the the generalized shear modulus and the transient density correlator.Comment: 21 pages, 13 figure

Thermophoresis of thermoresponsive polystyrene-poly(N-isopropylacrylamide) core-shell particles

We have investigated diffusion and thermodiffusion of thermosensitive core shell particles PS PNIPAM that consist of a poly styrene PS core and a poly N isopropyl acrylamide PNIPAM shell by means of an optical beam deflection technique. The results are compared to recent literature values for linear PNIPAM chains and cross linked PNIPAM microgel particles. The temperature dependence of the thermodiffusion coefficient of the core shell colloids resembles that of the linear polymer and a number of other aqueous systems. It is significantly different from one of the crosslinked microgel

Nonlinear rheology of glass-forming colloidal dispersions : transient stress-strain relations from anisotropic mode coupling theory and thermosensitive microgels

Transient stress-strain relations close to the colloidal glass transition are obtained within the integration through transients framework generalizing mode coupling theory to flow driven systems. Results from large-scale numerical calculations are quantitatively compared to experiments on thermosensitive microgels, which reveals that theory captures the magnitudes of stresses semi-quantitatively even in the nonlinear regime, but overestimates the characteristic strain where plastic events set in. The former conclusion can also be drawn from flow curves, while the latter conclusion is supported by a comparison to single particle motion measured by confocal microscopy. The qualitative picture, as previously obtained from simplifications of the theory in schematic models, is recovered by the quantitative solutions of the theory for Brownian hard spheres

Thermosensitive core-shell particles as model systems for studying the flow behavior of concentrated colloidal dispersions

We report on a comprehensive investigation of the flow behavior of colloidal thermosensitive core-shell particles at high densities. The particles consist of a solid core of poly(styrene) onto which a network of cross-linked poly (N-isopropylacrylamide) is affixed. Immersed in water the shell of these particles will swell if the temperature is low. Raising the temperature above 32 °C leads to a volume transition within this shell which leads to a marked shrinking of the shell. The particles have well-defined core-shell structure and a narrow size distribution. The remaining electrostatic interactions due to a small number of charges affixed to the core particles can be screened by adding 0.05M KCl to the suspensions. Below the lower critical solution temperature at 32 °C the particles are purely repulsive. Above this transition, a thermoreversible coagulation takes place. Lowering the temperature again leads to full dissociation of the aggregates formed by this process. The particles crystallize for effective volume fractions between 0.48 and 0.55. The crystallites can be molten by shear in order to reach a fluid sample again. The reduced shear stressmeasured in this metastable disordered state was found to be a unique function of the shear rate and the effective volume fraction. These reduced flow curves thus obtained can be described quantitatively by the theory of Fuchs and Cates which is based on the mode-coupling theory of the glass transition

Direct imaging of temperature-sensitive core-shell latexes by cryogenic transmission electron microscopy

We present a comprehensive investigation of the volume transition in thermosensitive core-shell particles. The particles consist of a solid core of poly (styrene) (radius: 52 nm) onto which a network of crosslinked poly(N-isopropylacrylamide) (PNIPAM) is affixed. The degree of crosslinking of the PNIPAM shell effected by the crosslinker N,N'-methylenebisacrylamide was varied between 1.25 and 5 mol%. Immersed in water, the shell of these particles is swollen at low temperatures. Raising the temperature above 32◦C leads to a volume transition within the shell. Cryogenic transmission electron microscopy (Cryo-TEM) and dynamic light scattering (DLS) have been used to investigate the structure and swelling of the particles. The Cryo-TEM micrographs directly show inhomogeneities of the network. Moreover, a buckling of the shell from the core particle is evident. This buckling increases with decreasing degree of crosslinking. A comparison of the overall size of the particles determined by DLS and Cryo-TEM demonstrates that the hydrodynamic radius provides a valid measure for the size of the particles. The phase transition within the network measured by DLS can be described by the Flory–Rehner theory. It is shown that this model captures the main features of the volume transition within the core-shell particles including the dependence of the phase transition on the degree of crosslinking. All dispersions crystallize at volume fractions above 0.5. The resulting phase diagram is identical to the phase behavior of hard spheres within the limits of error. This demonstrates that the core-shell microgels can be treated as hard spheres up to volume fractions of at least 0.55