Equilibrium fluid-crystal interfacial free energy of bcc-crystallizing aqueous suspensions of polydisperse charged spheres.

The interfacial free energy is a central quantity in crystallization from the metastable melt. In suspensions of charged colloidal spheres, nucleation and growth kinetics can be accurately measured from optical experiments. In previous work, from these data effective nonequilibrium values for the interfacial free energy between the emerging bcc nuclei and the adjacent melt in dependence on the chemical potential difference between melt phase and crystal phase were derived using classical nucleation theory (CNT). A strictly linear increase of the interfacial free energy was observed as a function of increased metastability. Here, we further analyze these data for five aqueous suspensions of charged spheres and one binary mixture. We utilize a simple extrapolation scheme and interpret our findings in view of Turnbull's empirical rule. This enables us to present the first systematic experimental estimates for a reduced interfacial free energy, σ(0,bcc), between the bcc-crystal phase and the coexisting equilibrium fluid. Values obtained for σ(0,bcc) are on the order of a few k(B)T. Their values are not correlated to any of the electrostatic interaction parameters but rather show a systematic decrease with increasing size polydispersity and a lower value for the mixture as compared to the pure components. At the same time, σ(0) also shows an approximately linear correlation to the entropy of freezing. The equilibrium interfacial free energy of strictly monodisperse charged spheres may therefore be still greater.

Seed- and wall-induced heterogeneous nucleation in charged colloidal model systems under microgravity.

Understanding the process that drives an undercooled fluid to the crystal state is still a challenging issue for condensed matter physics and plays a key role in designing new materials. The crystallization kinetics and the resulting polycrystalline morphology are given by a complex interplay of crystal nucleation, growth, and ripening. A great deal of progress has been made in recent years using colloidal suspensions as model systems in the study of crystallization. Close analogies to atomic systems are observed which can be exploited to address questions not accessible in atomic solidification. Here we present systematic measurements of the crystallization kinetics of a charged colloidal model system adding small amounts of seeds using time resolved scattering techniques. Large seeds show strong sedimentation under gravity even on the time scale of the crystallization process. To avoid this problem we performed our measurements under microgravity during parabolic flights. We report how the seed size and structure affect crystal nucleation and growth as functions of metastability giving the possibility to modify the crystallization process and the resulting microstructure of the polycrystal.

Communications: Complete description of re-entrant phase behavior in a charge variable colloidal model system.

In titration experiments with NaOH, we have determined the full phase diagram of charged colloidal spheres in dependence on the particle density n, the particle effective charge Z(eff) and the concentration of screening electrolyte c using microscopy, light and ultrasmall angle x-ray scattering (USAXS). For sufficiently large n, the system crystallizes upon increasing Z(eff) at constant c and melts upon increasing c at only slightly altered Z(eff). In contrast to earlier work, equilibrium phase boundaries are consistent with a universal melting line prediction from computer simulation, if the elasticity effective charge is used. This charge accounts for both counterion condensation and many-body effects.

Colloids as model systems for metals and alloys: a case study of crystallization.

Metallic systems are widely used as materials in daily human life. Their properties depend very much on the production route. In order to improve the production process and even develop novel materials a detailed knowledge of all physical processes involved in crystallization is mandatory. Atomic systems like metals are characterized by very high relaxation rates, which make direct investigations of crystallization very difficult and in some cases impossible. In contrast, phase transitions in colloidal systems are very sluggish and colloidal suspensions are optically transparent. Therefore, colloidal systems are often discussed as model systems for metals. In the present work, we study the process of crystallization of charged colloidal systems from the very beginning. Charged colloids offer the advantage that the interaction potential can be systematically tuned by a variation of the particle number density and the salt concentration. We use light scattering and ultra-small angle x-ray scattering to investigate the formation of short-range order in the liquid state even far from equilibrium, crystal nucleation and crystal growth. The results are compared with those of equivalent studies on metallic systems. They are critically assessed as regards similarities and differences.

Enhanced crystal stability in a binary mixture of charged colloidal spheres.

We report on the phase behavior of a binary charged sphere mixture of size ratio Gamma=0.68 and charge ratio Lambda approximately 1 as a function of composition p and number density n . For p=0.1-0.3 we observe freezing at densities well below the freezing densities of the pure components. At all compositions our data indicate the formation of substitutional alloy crystals of body centered cubic structure. No indications for compound formation were observed. Rather, our findings point at the first observation of an upper azeotrope. Measurements of the crystallization kinetics reveal a combined density and composition dependence of growth velocities and nucleation rate densities, with small but significant anomalies at p*=0.2 . These correlated deviations can be rationalized within classical theories of solidification and suggest an increased similarity between melt and solid for this particular composition.

Colloids as model systems for liquid undercooled metals.

Charged colloidal particles interact via a hard core Yukawa potential, while isotropic Lennard-Jones-like potentials are frequently used as pair potentials in metals. We present measurements of the structure factor of shear molten monodisperse colloids and molten metals using ultrasmall-angle x-ray scattering and elastic neutron scattering, respectively. In both systems data analysis gives evidence of fivefold-symmetric short-range order becoming more pronounced with increasing deviations from equilibrium. The experiments demonstrate that in both systems topological effects control ordering in the melt state.

Competition between heterogeneous and homogeneous nucleation near a flat wall.

We studied the competition between heterogeneous and homogeneous nucleation of an aqueous suspension of charged colloidal spheres close to the container walls. Samples of equilibrium crystalline structure were shear-melted and the metastable melt left to solidify after the cessation of shear. The crystallization kinetics was monitored using time-resolved scattering techniques: at low particle number densities n we applied an improved static light scattering method while at large particle concentrations ultra-small-angle x-ray scattering was applied for the first time. Our results show some unexpected behavior: the heterogeneous nucleation at the container walls is delayed in comparison to the homogeneous bulk nucleation and its rate density appears surprisingly slightly smaller, demonstrating the complexity of the observed crystallization process.

Phase behaviour of deionized binary mixtures of charged colloidal spheres.

We review recent work on the phase behaviour of binary charged sphere mixtures as a function of particle concentration and composition. Both size ratios Γ and charge ratios Λ are varied over a wide range. Unlike the case for hard spheres, the long-ranged Coulomb interaction stabilizes the crystal phase at low particle concentrations and shifts the occurrence of amorphous solids to particle concentrations considerably larger than the freezing concentration. Depending on Γ and Λ, we observe upper azeotrope, spindle, lower azeotrope and eutectic types of phase diagrams, all known well from metal systems. Most solids are of body centred cubic structure. Occasionally stoichiometric compounds are formed at large particle concentrations. For very low Γ, entropic effects dominate and induce a fluid-fluid phase separation. Since for charged spheres the charge ratio Λ is also decisive for the type of phase diagram, future experiments with charge variable silica spheres are suggested.

Nucleation kinetics in deionized charged colloidal model systems: a quantitative study by means of classical nucleation theory.

We have studied the nucleation kinetics of charged colloidal model systems under salt free conditions crystallizing in bcc structure covering a wide range of particle number densities 18 microm(-3) < or =n< or =66.3 microm(-3). We employed direct video-microscopic observation of individual nucleation events to obtain time resolved nucleation rate densities. Polarization microscopy and static light scattering on the resulting solids in combination with Avrami theory is used to determine the steady state nucleation rate at high undercoolings. The final nucleation rate densities J from different methods are observed to be consistent with each other. By increasing the difference in the chemical potential between melt and crystal Delta mu about one order of magnitude J increases from 10(9)m(-3)s(-1) to 10(17)m(-3)s(-1) over approximately seven orders of magnitude. The data can be well analyzed and interpreted using classical nucleation theory (CNT) leading to a linearly increasing melt-crystal surface tension. Surprisingly, the reduced surface tension is about one order of magnitude larger compared to other system (metals; hard sphere colloids). The critical radius of the crystal nuclei is decreasing down to a very small value of 1.5 coordination shells. The determined kinetic prefactors are up to 10 orders of magnitude smaller than the prefactor calculated by CNT.

Microscopic investigations of homogeneous nucleation in charged sphere suspensions.

We studied the homogeneous nucleation kinetics of an aqueous suspension of charged colloidal spheres under de-ionized conditions. Samples of equilibrium crystalline structure were shear molten and the metastable melt left to solidify after cessation of shear. At low particle number densities n, corresponding to low metastability of the melt, nucleation was monitored directly via video microscopy. We determined the nucleation rates gamma(t) by counting the number of newly appearing crystals in the observation volume per unit time. Using a suitable discrete adaptation of Avrami's [J. Chem. Phys. 7, 1003 (1939); ibid.8, 212 (1940); ibid.9, 177 (1941)] model for solidification via homogeneous nucleation and subsequent growth, we calculate the remaining free volume VF(t) to obtain the rate densities J(t) = gamma(t)/VF(t). We observe J(t) to rise steeply, display a plateau at a maximum rate density Jmax, and to decrease again. With increased n the plateau duration shrinks while Jmax increases. At low to moderate number densities fully solidified samples were analyzed by microscopy to obtain the grain-size distribution and the average crystallite size angle brackets(L). Under the assumption of stationarity, we obtained the nucleation rate density J(Avr), which increased strongly with increasing n. Interestingly, J(Avr) agrees quantitatively to Jmax and to J(Avr) as obtained previously from scattering data taken on the same sample at large n. Thus, by combination of different methods, reliable nucleation rate densities are now available over roughly one order of magnitude in n and eight orders of magnitude in J.

Drude-type conductivity of charged sphere colloidal crystals: density and temperature dependence.

We report on extensive measurements in the low-frequency limit of the ac conductivity of colloidal fluids and crystals formed from charged colloidal spheres suspended in de-ionized water. Temperature was varied in a range of 5 degrees C < Theta < 35 degrees C and the particle number density n between 0.2 and 25 microm(-3) for the larger, respectively, 2.75 and 210 microm(-3) for the smaller of two investigated species. At fixed Theta the conductivity increased linearly with increasing n without any significant change at the fluid-solid phase boundary. At fixed n it increased with increasing Theta and the increase was more pronounced for larger n. Lacking a rigorous electrohydrodynamic treatment for counterion-dominated systems we describe our data with a simple model relating to Drude's theory of metal conductivity. The key parameter is an effectively transported particle charge or valence Z(*). All temperature dependencies other than that of Z(*) were taken from literature. Within experimental resolution Z(*) was found to be independent of n irrespective of the suspension structure. Interestingly, Z(*) decreases with temperature in near quantitative agreement with numerical calculations.

Crystallization in charged two-component suspensions.

We report on the crystallization of colloidal crystals comprising of charged particles with different size ratio dispersed in thoroughly deionized water. Single components were characterized carefully and their nucleation behavior was investigated before the preparation of mixtures. Mixtures investigated at constant particle number densities showed body centred cubic structure, conductivity, and shear moduli comply with the assumption of a randomly substituted crystal. Most importantly, for the first time we obtain the dependence of the nucleation rate densities in dependence on the composition and (for one fixed composition) the particle number density. The process of nucleation in random substitutional crystals is found to be similar to the one-component case.