Abstract. We present a comprehensive rheological study of a suspension of thermosensitive particles dispersed in water. The volume fraction of these particles can be adjusted by the temperature of the system in a continuous fashion. Due to the finite polydispersity of the particles (standard deviation: 17%), crystallization is suppressed and no fluid-crystal transition intervenes. Hence, the moduli G ′ and G ′′ in the linear viscoelastic regime as well as the flow curves (shear stress σ (γ) as the function of the shear rateγ) could be measured in the fluid region up to the vicinity of the glass transition. Moreover, flow curves could be obtained over a range of shear rates of 8 orders of magnitude while G ′ and G ′′ could be measured spanning over 9 orders of magnitude. Special emphasis has been laid on precise measurements down to the smallest shear rates/frequencies. It is demonstrated that mode-coupling theory generalized in the integration through transients framework provides a full description of the flow curves as well as the viscoelastic behavior of concentrated suspensions with a single set of well-defined parameters.

We consider a model dense colloidal dispersion at the glass transition, and investigate the connection between equilibrium stress fluctuations, seen in linear shear moduli, and the shear stresses under strong flow conditions far from equilibrium, viz., flow curves for finite shear rates. To this purpose, thermosensitive core-shell particles consisting of a polystyrene core and a cross-linked poly(N-isopropylacrylamide) shell were synthesized. Data over an extended range in shear rates and frequencies are compared to theoretical results from integrations through transients and mode coupling approaches. The connection between nonlinear rheology and glass transition is clarified. While the theoretical models semiquantitatively fit the data taken in fluid states and the predominant elastic response of glass, a yet unaccounted dissipative mechanism is identified in glassy states.

Using a combination of theory, experiment and simulation we investigate the nonlinear response of dense colloidal suspensions to large amplitude oscillatory shear flow. The time-dependent stress response is calculated using a recently developed schematic mode-coupling-type theory describing colloidal suspensions under externally applied flow. For finite strain amplitudes the theory generates a nonlinear response, characterized by significant higher harmonic contributions. An important feature of the theory is the prediction of an ideal glass transition at sufficiently strong coupling, which is accompanied by the discontinuous appearance of a dynamic yield stress. For the oscillatory shear flow under consideration we find that the yield stress plays an important role in determining the non linearity of the time-dependent stress response. Our theoretical findings are strongly supported by both large amplitude oscillatory (LAOS) experiments (with FT-rheology analysis) on suspensions of thermosensitive core-shell particles dispersed in water and Brownian dynamics simulations performed on a two-dimensional binary hard-disc mixture. In particular, theory predicts nontrivial values of the exponents governing the final decay of the storage and loss moduli as a function of strain amplitude which are in excellent agreement with both simulation and experiment. A consistent set of parameters in the presented schematic model achieves to jointly describe linear moduli, nonlinear flow curves and large amplitude oscillatory spectroscopy.

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 poly͑styrene͒ onto which a network of cross-linked poly͑N-isopropylacrylamide͒ 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 stress measured 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 ͓Phys. Rev. Lett. 89, 248304 ͑2002͔͒ which is based on the mode-coupling theory of the glass transition.

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.