242 research outputs found
Small changes in particle-size distribution dramatically delay and enhance nucleation in hard sphere colloidal suspensions
We present hard-sphere crystallization kinetics for three samples with small differences in polydispersity. We show that an increase in polydispersity of 1% is sufficient to cause dramatic changes in the crystallization kinetics: Crystallization is delayed by almost one decade in time and quantitative and qualitative changes in the crystallization scenario are observed. Surprisingly the nucleation rate density is enhanced by almost a factor of 10. We interpret these results in terms of polydispersity limited growth, where local fractionation processes lead to a delayed but faster nucleation
Crystallization of hard-sphere colloids: deviations from classical nucleation theory
The creation of three-dimensional ordered colloidal crystals, for application in a range of nanotechnologies, has been a goal for many researchers in the past few years. The main difficulty in creating macroscopic sized crystals of densely packed colloidal particles is that colloidal particles always have a range of particle sizes - ie, they are polydisperse. This paper studied the crystallization kinetics of a hard-sphere colloid with a well defined Gaussian polydispersity. The authors find that crystallization occurs in two stages, and does not follow the simple classical nucleation picture. The paper discusses the implications of these results for research into colloidal crystals as possible nano-materials
Effect of polydispersity on the crystallization kinetics of suspensions of colloidal hard spheres when approaching the glass transition
We present a comprehensive study of the solidification scenario in suspensions of colloidal hard spheres for three polydispersities between 4.8% and 5.8%, over a range of volume fractions from near freezing to near the glass transition. From these results, we identify four stages in the crystallization process: (i) an induction stage where large numbers of precursor structures are observed, (ii) a conversion stage as precursors are converted to close packed structures, (iii) a nucleation stage, and (iv) a ripening stage. It is found that the behavior is qualitatively different for volume fractions below or above the melting volume fraction. The main effect of increasing polydispersity is to increase the duration of the induction stage, due to the requirement for local fractionation of particles of larger or smaller than average size. Near the glass transition, the nucleation process is entirely frustrated, and the sample is locked into a compressed crystal precursor structure. Interestingly, neither polydispersity nor volume fraction significantly influences the precursor stage, suggesting that the crystal precursors are present in all solidifying samples. We speculate that these precursors are related to the dynamical heterogeneities observed in a number of dynamical studies
Asymptotic laws for tagged-particle motion in glassy systems
Within the mode-coupling theory for structural relaxation in simple systems
the asymptotic laws and their leading-asymptotic correction formulas are
derived for the motion of a tagged particle near a glass-transition
singularity. These analytic results are compared with numerical ones of the
equations of motion evaluated for a tagged hard sphere moving in a hard-sphere
system. It is found that the long-time part of the two-step relaxation process
for the mean-squared displacement can be characterized by the -relaxation-scaling law and von Schweidler's power-law decay while the
critical-decay regime is dominated by the corrections to the leading power-law
behavior. For parameters of interest for the interpretations of experimental
data, the corrections to the leading asymptotic laws for the non-Gaussian
parameter are found to be so large that the leading asymptotic results are
altered qualitatively by the corrections. Results for the non-Gaussian
parameter are shown to follow qualitatively the findings reported in the
molecular-dynamics-simulations work by Kob and Andersen [Phys. Rev. E 51, 4626
(1995)]
Preparation and characterization of particles with small differences in polydispersity
Colloidal particles are widely used both in fundamental research and in materials science. One important parameter influencing the physical properties of colloidal materials is the particle size distribution (polydispersity) of the colloidal particles. Recent work on colloidal crystallization has demonstrated that even subtle changes in polydispersity can have significant effects. In this study we present centrifugation techniques for subtly manipulating the width and the shape of the particle size distribution, for polydispersities less than 10%. We use scanning electron microscopy as well as dynamic and static light scattering to characterize the particle size distributions. We compare the results and highlight the difficulties associated with the determination of accurate particle size distributions
A quantitative test of the mode-coupling theory of the ideal glass transition for a binary Lennard-Jones system
Using a molecular dynamics computer simulation we determine the temperature
dependence of the partial structure factors for a binary Lennard-Jones system.
These structure factors are used as input data to solve numerically the
wave-vector dependent mode-coupling equations in the long time limit. Using the
so determined solutions, we compare the predictions of mode-coupling theory
(MCT) with the results of a previously done molecular dynamics computer
simulation [Phys. Rev. E 51, 4626 (1995), ibid. 52, 4134 (1995)]. From this
comparison we conclude that MCT gives a fair estimate of the critical coupling
constant, a good estimate of the exponent parameter, predicts the wave-vector
dependence of the various nonergodicity parameters very well, except for very
large wave-vectors, and gives also a very good description of the space
dependence of the various critical amplitudes. In an attempt to correct for
some of the remaining discrepancies between the theory and the results of the
simulation, we investigate two small (ad hoc) modifications of the theory. We
find that one modification gives a worse agreement between theory and
simulation, whereas the second one leads to an improved agreement.Comment: Figures available from W. Ko
Dynamics of hard-sphere suspension using Dynamic Light Scattering and X-Ray Photon Correlation Spectroscopy: dynamics and scaling of the Intermediate Scattering Function
Intermediate Scattering Functions (ISF's) are measured for colloidal hard
sphere systems using both Dynamic Light Scattering (DLS) and X-ray Photon
Correlation Spectroscopy (XPCS). We compare the techniques, and discuss the
advantages and disadvantages of each. Both techniques agree in the overlapping
range of scattering vectors. We investigate the scaling behaviour found by
Segre and Pusey [1] but challenged by Lurio et al. [2]. We observe a scaling
behaviour over several decades in time but not in the long time regime.
Moreover, we do not observe long time diffusive regimes at scattering vectors
away from the peak of the structure factor and so question the existence of a
long time diffusion coefficients at these scattering vectors.Comment: 21 pages, 11 figure
Higher order glass-transition singularities in colloidal systems with attractive interactions
The transition from a liquid to a glass in colloidal suspensions of particles
interacting through a hard core plus an attractive square-well potential is
studied within the mode-coupling-theory framework. When the width of the
attractive potential is much shorter than the hard-core diameter, a reentrant
behavior of the liquid-glass line, and a glass-glass-transition line are found
in the temperature-density plane of the model. For small well-width values, the
glass-glass-transition line terminates in a third order bifurcation point, i.e.
in a A_3 (cusp) singularity. On increasing the square-well width, the
glass-glass line disappears, giving rise to a fourth order A_4 (swallow-tail)
singularity at a critical well width. Close to the A_3 and A_4 singularities
the decay of the density correlators shows stretching of huge dynamical
windows, in particular logarithmic time dependence.Comment: 19 pages, 12 figures, Phys. Rev. E, in prin
Aspects of the dynamics of colloidal suspensions: Further results of the mode-coupling theory of structural relaxation
Results of the idealized mode-coupling theory for the structural relaxation
in suspensions of hard-sphere colloidal particles are presented and discussed
with regard to recent light scattering experiments. The structural relaxation
becomes non-diffusive for long times, contrary to the expectation based on the
de Gennes narrowing concept. A semi-quantitative connection of the wave vector
dependences of the relaxation times and amplitudes of the final
-relaxation explains the approximate scaling observed by Segr{\`e} and
Pusey [Phys. Rev. Lett. {\bf 77}, 771 (1996)]. Asymptotic expansions lead to a
qualitative understanding of density dependences in generalized Stokes-Einstein
relations. This relation is also generalized to non-zero frequencies thereby
yielding support for a reasoning by Mason and Weitz [Phys. Rev. Lett {\bf 74},
1250 (1995)]. The dynamics transient to the structural relaxation is discussed
with models incorporating short-time diffusion and hydrodynamic interactions
for short times.Comment: 11 pages, 9 figures; to be published in Phys. Rev.
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