Search results for "THERMODYNAMICS"
showing 10 items of 2774 documents
Experimental determination of effective charges in aqueous suspensions of colloidal spheres
2003
Abstract We determined the low frequency conductivity σ , the phase behaviour and the shear modulus G of colloidal fluids, respectively solids prepared from deionised aqueous suspensions of highly charged spherical particles. Conductivity measures the number of freely moving small ions Z * σ and thus relates to the ion condensation process in the electric double layer under conditions of finite macro-ion concentrations. Phase behaviour and elasticity data are consistently described by a Debye–Huckel pair potential assuming pair-wise additive macro-ion interactions. Like Z * σ , also the effective charges Z * G derived from the elasticity data scales with the ratio of macro-ion radius to Bje…
Mechanisms for the Decay of Unstable and Metastable Phases: Spinodal Decomposition, Nucleation and Late-Stage Coarsening
1989
The basic concepts on the kinetics of phase separation in alloys are introduced, and the current status of the theory is briefly reviewed. Particular emphasis is given to questions such as the conditions under which the linearized theory of spinodal decomposition is valid, the significance of spinodal curves, the possible description of coarsening in terms of power laws and structure-factor scaling, and non-equilibrium percolation phenomena.
Approaching the limits of multiple scattering decorrelation: 3D light-scattering apparatus utilising semiconductor lasers
2007
Light scattering as a function of scattering angle can be regarded as a standard method to investigate the dynamics of dilute colloidal suspensions. Concentrated suspensions, which are of interest if interactions between the particles are to be investigated, usually show strong multiple scattering. Decorrelation of multiple scattered light, which isolates single scattering events at the expense of a reduced signal-to-noise ratio, has been proven to work using the two-colour crosscorrelation scheme.
Relation of Interdiffusion and Self-Diffusion in Polymer Mixtures
1986
From different assumptions one obtains linear relationships either between the interdiffusion coefficient and the self-diffusion coefficients or between the inverse interdiffusion coefficient and the inverse self-diffusion coefficients. The nature of these assumptions and possible experiments for discriminating between them are discussed.
Making Floryr–Huggins Practical: Thermodynamics of Polymer-Containing Mixtures
2010
The theoretical part of this article demonstrates how the original Flory–Huggins theory can be extended to describe the thermodynamic behavior of polymer-containing mixtures quantitatively. This progress is achieved by accounting for two features of macromolecules that the original approach ignores: the effects of chain connectivity in the case of dilute solutions, and the ability of polymer coils to change their spatial extension in response to alterations in their molecular environment. In the general case, this approach leads to composition-dependent interaction parameters, which can for most binary systems be described by means of two physically meaningful parameters; systems involving …
Solubility of Polymers
2011
Detailed knowledge concerning the phase state (homogeneous or coexistence of two or more condensed phases) of polymer containing mixtures is indispensible in virtually any area related to the production or application of macromolecules. In addition to this qualitative information it is for many purposes highly desirable to dispose of quantitative data regarding solvent quality or, more generally, with respect to the thermodynamic interaction between the components of the mixtures. This contribution starts with a brief presentation of the thermodynamic criteria deciding on the phase state and presents the experimental methods used in this area. The next section gives an overview on typical b…
Entropy of glassy polymer melts: Comparison between Gibbs-DiMarzio theory and simulation.
1996
We calculate the free energy of a model for a polymer melt in a computer simulation of the bond-fluctuation model and determine the entropy of the melt over a wide range of temperatures, including the region close to the glass transition. The results are compared with the Gibbs-DiMarzio theory, a theory by Flory for semiflexible polymers, and a modification of their theories due to Milchev. We can describe the data within the framework of the Flory theory with Milchev's correction and discuss the consequences for the understanding of the glass transition. \textcopyright{} 1996 The American Physical Society.
Heterogeneous nucleation at a wall near a wetting transition: a Monte Carlo test of the classical theory
2009
While for a slightly supersaturated vapor the free energy barrier ΔF(hom)(*), which needs to be overcome in a homogeneous nucleation event, may be extremely large, nucleation is typically much easier at the walls of the container in which the vapor is located. While no nucleation barrier exists if the walls are wet, for incomplete wetting of the walls, described via a nonzero contact angle Θ, classical theory predicts that nucleation happens through sphere-cap-shaped droplets attracted to the wall, and their formation energy is ΔF(het)(*) = ΔF(hom)(*)f(Θ), with f(Θ) = (1-cosΘ)(2)(2+cosΘ)/4. This prediction is tested through simulations for the simple cubic lattice gas model with nearest-nei…
Dynamic Anomalies and their Relation to the Glass Transition: A Neutron Scattering Study of the Glass Forming Van der Waals Liquid Ortho-terphenyl
1991
Neutron scattering experiments on the molecular glass former ortho-terphenyl reveal a dynamic anomaly at a temperature Tc ≈ 290 K well above the calorimetric glass temperature Tg = 243 K. Close above Tc the density autocorrelation function ΦQ(t) shows a two step decay over 4–5 decades in time. The slower component obeys the time-temperature superposition principle. Its line shape can be well parametrized by a Kohlrausch law and is strongly temperature dependent as its relaxation time scales with the shear viscosity. Thus this component is identified with the structural relaxation (α-process). The faster component (β-process) is much less temperature dependent. Its line shape factorizes in a…
Testing Mode-Coupling Theory for a Supercooled Binary Lennard-Jones Mixture I: The van Hove Correlation Function
1995
We report the results of a large scale computer simulation of a binary supercooled Lennard-Jones liquid. We find that at low temperatures the curves for the mean squared displacement of a tagged particle for different temperatures fall onto a master curve when they are plotted versus rescaled time $tD(T)$, where $D(T)$ is the diffusion constant. The time range for which these curves follow the master curve is identified with the $\alpha$-relaxation regime of mode-coupling theory (MCT). This master curve is fitted well by a functional form suggested by MCT. In accordance with idealized MCT, $D(T)$ shows a power-law behavior at low temperatures. The critical temperature of this power-law is t…