RESUMO
We have investigated concentrated suspensions of polydisperse hard spheres and have determined the dynamics and sizes of individual particles using confocal microscopy. With increasing concentration, the dynamics of the small and large particles start to differ. The large particles exhibit slower dynamics and stronger localization. Moreover, as the particle size increases, the local volume fraction Ï_{loc} also increases. In the glass state, the localization length significantly decreases beyond Ï_{loc}≈0.67. This suggests a link between local crowding and dynamical heterogeneities. However dynamical arrest of subpopulations seems not directly linked to a large value of Ï_{loc}, indicating the importance of collective effects.
RESUMO
Glasses exhibit a liquidlike structure but a solidlike rheological response with plastic deformations only occurring beyond yielding. Thus, predicting the rheological behavior from the microscopic structure is difficult, but important for materials science. Here, we consider colloidal suspensions and propose to supplement the static structural information with the local dynamics, namely, the rearrangement and breaking of the cage of neighbors. This is quantified by the mean squared nonaffine displacement and the number of particles that remain nearest neighbors for a long time, i.e., long-lived neighbors, respectively. Both quantities are followed under shear using confocal microscopy and are the basis to calculate the affine and nonaffine contributions to the elastic stress, which is complemented by the viscoelastic stress to give the total stress. During start-up of shear, the model predicts three transient regimes that result from the interplay of affine, nonaffine, and viscoelastic contributions. Our prediction quantitatively agrees with rheological data and their dependencies on volume fraction and shear rate.
RESUMO
The history dependence of glasses formed from flow-melted steady states by a sudden cessation of the shear rate γ[over Ë] is studied in colloidal suspensions, by molecular dynamics simulations and by mode-coupling theory. In an ideal glass, stresses relax only partially, leaving behind a finite persistent residual stress. For intermediate times, relaxation curves scale as a function of γ[over Ë]t, even though no flow is present. The macroscopic stress evolution is connected to a length scale of residual liquefaction displayed by microscopic mean-squared displacements. The theory describes this history dependence of glasses sharing the same thermodynamic state variables but differing static properties.
RESUMO
Crystals of partially neutralized stearic acid with triethanolamine (TEA) were prepared by mixing these two materials above 80 degrees C and then cooling. The crystalline composition and the structure and melting behavior of the resultant products were characterized with small-angle and wide-angle X-ray diffraction, thermal analysis, microscopy, and infrared spectroscopy. It was discovered that an acid-soap complex of 2:1 fixed stoichiometric ratio exists between stearic acid and TEA stearate. A binary phase diagram of stearic acid and TEA soap is built based on the experimental results; this is the first published record of a binary phase diagram for amine-based soap. Its behavior is significantly different from that of binary systems of fatty acid and alkali soap.
Assuntos
Etanolaminas/química , Sabões/química , Ácidos Esteáricos/química , Ácidos/química , Cristalização , Cristalografia por Raios X , Temperatura Alta , Raios Infravermelhos , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura , Difração de Raios XRESUMO
A combination of confocal microscopy and rheology experiments, Brownian dynamics (BD) and molecular dynamics (MD) simulations and mode coupling theory (MCT) have been applied in order to investigate the effect of shear rate on the transient dynamics and stress-strain relations in supercooled and glassy systems under shear. Immediately after shear is switched on, the microscopic dynamics display super-diffusion and the macroscopic rheology a stress overshoot, which become more pronounced with increasing shear rate. MCT relates both to negative sections of the generalized shear modulus, which grow with increasing shear rate. When the inverse shear rate becomes much smaller than the structural relaxation time of the quiescent system, relaxation through Brownian motion becomes less important. In this regime, larger stresses are accumulated before the system yields and the transition from localization to flow occurs earlier and more abruptly.