Hard spheres ordering transitions

The entropically driven disorder-order transition in hard-sphere fluids was originally discovered in computer simulations [58, 59]. The development of colloidal suspensions behaving as hard spheres (i.e., having negligible Hamaker constants, see Section VI-3) provided the means to experimentally verify the transition. Experimental data on the nucleation of hard-sphere colloidal crystals [60] allows one to extract the hard-sphere solid-liquid interfacial tension, 7 = 0.55 0.02k T/o, where a is the hard-sphere diameter [61]. This value agrees well with that found from density functional theory, 7 = 0.6 0.02k r/a 2 [21] (Section IX-2A). 

Charged particles in polar solvents have soft-repulsive interactions (see section C2.6.4). Just as hard spheres, such particles also undergo an ordering transition. Important differences, however, are that tire transition takes place at (much) lower particle volume fractions, and at low ionic strengtli (low k) tire solid phase may be body centred cubic (bee), ratlier tlian tire more compact fee stmcture (see [69, 73, 84]). For tire interactions, a Yukawa potential (equation (C2.6.11)1 is often used. The phase diagram for the Yukawa potential was calculated using computer simulations by Robbins et al [851. 

We will focus on one experimental study here. Monovoukas and Cast studied polystyrene particles witli a = 61 nm in potassium chloride solutions [86]. They obtained a very good agreement between tlieir observations and tire predicted Yukawa phase diagram (see figure C2.6.9). In order to make tire comparison tliey rescaled the particle charges according to Alexander et al [43] (see also [82]). At high electrolyte concentrations, tire particle interactions tend to hard-sphere behaviour (see section C2.6.4) and tire phase transition shifts to volume fractions around 0.5 [88]. 

Although Eqs. (33), (34), and especially (35), are useful they have a problem. They all predict that the hard sphere system is a fluid until = 1. This is beyond close packing and quite impossible. In fact, hard spheres undergo a first order phase transition to a solid phase at around pd 0.9. This has been estabhshed by simulations [3-5]. To a point, the BGY approximation has the advantage here. As is seen in Fig. 1, the BGY equation does predict that dp dp)j = 0 at high densities. However, the location of the transition is quite wrong. Another problem with the PY theory is that it can lead to negative values of g(r). This is a result of the linearization of y(r) - 1 that... 

An intrinsic surface is built up between both phases in coexistence at a first-order phase transition. For the hard sphere crystal-melt interface [51] density, pressure and stress profiles were calculated, showing that the transition from crystal to fluid occurs over a narrow range of only two to three crystal layers. Crystal growth rate constants of a Lennard-Jones (100) surface [52] were calculated from the fluctuations of interfaces. There is evidence for bcc ordering at the surface of a critical fee nucleus [53]. 

This is strong evidence for assuming that dispersions of ideal hard spheres would be expected to show a transition in the viscous behaviour between

short time selfdiffusion coefficient Z)s. This still shows a significant value after the order-disorder transition. The problem faced by the rheologist in interpreting hard sphere systems is that at high concentrations there is... 

FIG. 14 Phase diagram of a system of hard-spheres between two parallel walls. In the three-dimensional limit (/c -> oo) the system is fluid-like for 3D < 0.5. When the walls separation is comparable to the particles size (/c 1) the system can undergo disorder-order phase transition. Adapted from Chavez-Paez et al. [39]. 

Tc. The two power-law exponents are not independent but depend on a single parameter, the so-called critical exponent X, which is specific for a given interaction potential (e.g., hard spheres). Actually, the interaction potential enters the MCT equations only indirectly via the structure factor S(q), which fixes the nonlinear coupling in the generalized oscillator equation. It is important to note that the MCT exponents are not universal in contrast to those of second-order phase transitions. In the case of hard spheres, for example, S(q) can be calculated via the Percus-Yevick approximation [26], and the full time and -dependence of < >(q. f) were obtained. As an example, Fig. 10 shows the susceptibility spectra of the hard-sphere system at a particular q. Note that temperature cannot be defined in the hard-sphere system instead, the packing fraction cp is used as a parameter. Above the critical packing fraction 0), which corresponds to T < Tc in systems where T exists, the a-process is absent (frozen) and only the fast dynamics is present. At cp < tpc the a-peak and the concomitant susceptibility minimum shift to lower frequencies with increasing cp, so that the closer cp is to the critical value fast dynamics can be identified (curve c in Fig. 10). 

FIGURE 11.10 Gibbs free energy, G, versus osmotic pressure, II, for a suspension of hard spheres showing the intersection of the disordered and the ordered curves corresponding to the disorder-order transition with 4a-a%/3 = 0.74. Adapted from Cast et al. [63]. Reprinted with permission Academic Press. 

Crystalline or orientational orderings are mostly controlled by repulsive forces, such as excluded-volume forces. The crystalline transitions in ideal hard-sphere fluids and the nematic liquid crystalline transitions in hard-rod suspensions are convenient simple models of corresponding transitions in fluids composed of uncharged spherical or elongated molecules or particles. The transition from the isotropic to the nematic state can be described theoretically using the Onsager, Maier-Saupe, or Rory theories. 

Figure 7.4 Phase diagram for adhesive hard spheres as a function of Baxter temperature rg. The solid line is the spinodal line for liquid-liquid phase separation (the dense liquid phase is probably metastable), the dot-dashed line is the freezing line for appearance of an ordered packing of spheres, and the dashed line is the percolation transition. (Adapted from Grant and Russel 1993, reprinted with permission from the American Physical Society.)...

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