David Hajnal

Shear stresses of colloidal dispersions at the glass transition in equilibrium and in flow

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.

Glass Transition in Confined Geometry

Extending mode-coupling theory, we elaborate a microscopic theory for the glass transition of liquids confined between two parallel flat hard walls. The theory contains the standard mode-coupling theory equations in bulk and in two dimensions as limiting cases and requires as input solely the equilibrium density profile and the structure factors of the fluid in confinement. We evaluate the phase diagram as a function of the distance of the plates for the case of a hard sphere fluid and obtain an oscillatory behavior of the glass transition line as a result of the structural changes related to layering.

Flow curves of colloidal dispersions close to the glass transition - Asymptotic scaling laws in a schematic model of mode coupling theory

The flow curves, viz. the curves of stationary stress under steady shearing, are obtained close to the glass transition in dense colloidal dispersions using asymptotic expansions in the schematic

Tests of mode-coupling theory in two dimensions

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Effect of mixing and spatial dimension on the glass transition

-model of mode coupling theory. The shear thinning of the viscosity in fluid states and the yielding of glassy states is discussed. At the transition between fluid and shear-molten glass, simple and generalized Herschel-Bulkley laws are derived with power law exponents that can be computed for different particle interactions from the equilibrium structure factor.

Delocalization-localization transition due to anharmonicity.

We analyze the glassy dynamics of binary mixtures of hard disks in two dimensions. Predictions of the mode-coupling theory (MCT) are tested with extensive Brownian dynamics simulations. Measuring the collective particle density correlation functions in the vicinity of the glass transition, we verify four predicted mixing effects. For instance, for large size disparities, adding a small amount of small particles at a fixed packing fraction leads to a speedup in the long-time dynamics, while for small size disparities it leads to a slowing-down. Qualitative features of the nonergodicity parameters and the β relaxation, which both depend in a nontrivial way on the mixing ratio, are found in the simulated correlators. Studying one system in detail, we are able to determine its ideal MCT glass transition point as φ(c)=0.7948 and test MCT predictions quantitatively.

Strain Pattern in Supercooled Liquids.

We study the influence of composition changes on the glass transition of binary hard disk and hard sphere mixtures in the framework of mode coupling theory. We derive a general expression for the slope of a glass transition line. Applied to the binary mixture in the low concentration limits, this method allows a fast prediction of some properties of the glass transition lines. The glass transition diagram we find for binary hard disks strongly resembles the random close packing diagram. Compared to three dimensions from previous studies, the extension of the glass regime due to mixing is much more pronounced in two dimensions where plasticization only sets in at larger size disparities. For small size disparities we find a stabilization of the glass phase quadratic in the deviation of the size ratio from unity.

Glass transition of binary mixtures of dipolar particles in two dimensions

Analytical and numerical calculations for a reduced Fermi-Pasta-Ulam chain demonstrate that energy localization does not require more than one conserved quantity. Clear evidence for the existence of a sharp delocalization-localization transition at a critical amplitude A_c is given. Approaching A_c from above and below, diverging time scales occur. Above A_c, the energy packet converges towards a discrete breather. Nevertheless, ballistic energy transportation is present, demonstrating that its existence does not necessarily imply delocalization.

Shear moduli of two dimensional binary glasses

Investigations of strain correlations at the glass transition reveal unexpected phenomena. The shear strain fluctuations show an Eshelby-strain pattern [∼cos(4θ)/r^{2}], characteristic of elastic response, even in liquids, at long times. We address this using a mode-coupling theory for the strain fluctuations in supercooled liquids and data from both video microscopy of a two-dimensional colloidal glass former and simulations of Brownian hard disks. We show that the long-ranged and long-lived strain signatures follow a scaling law valid close to the glass transition. For large enough viscosities, the Eshelby-strain pattern is visible even on time scales longer than the structural relaxation time τ and after the shear modulus has relaxed to zero.

Theory of thermodynamic stresses in colloidal dispersions at the glass transition

Abstract We study the glass transition of binary mixtures of dipolar particles in two dimensions within the framework of mode-coupling theory, focusing in particular on the influence of composition changes. In a first step, we demonstrate that the experimental system of Konig et al. [Eur. Phys. J. E 18, 287 (2005)] is well described by point dipoles through a comparison between the experimental partial structure factors and those from our Monte Carlo simulation. For such a mixture of point particles we show that there is always a plasticization effect, i.e. a stabilization of the liquid state due to mixing, in contrast to binary hard disks. We demonstrate that the predicted plasticization effect is in qualitative agreement with experimental results. Furthermore, also some general properties of the glass transition lines are discussed.