Salt-concentration-dependent nucleation rates in low-metastability colloidal charged sphere melts containing small amounts of doublets.

We determined bulk crystal nucleation rates in aqueous suspensions of charged spheres at low metastability. Experiments were performed in dependence on electrolyte concentration and for two different particle number densities. The time-dependent nucleation rate shows a pronounced initial peak, while postsolidification crystal size distributions are skewed towards larger crystallite sizes. At each concentration, the nucleation rate density initially drops exponentially with increasing salt concentration. The full data set, however, shows an unexpected scaling of the nucleation rate densities with metastability times the number density of particles. Parameterization of our results in terms of classical nucleation theory reveals unusually low interfacial free energies of the nucleus surfaces and nucleation barriers well below the thermal energy. We tentatively attribute our observations to the presence of doublets introduced by the employed conditioning technique. We discuss the conditions under which such small seeds may induce nucleation.

Formation of Laves phases in buoyancy matched hard sphere suspensions.

Colloidal Laves phases (LPs) are promising precursors for photonic materials. Laves phases have not yet been observed to form in experiments on colloidal suspensions of hard spheres (HS), even though they have been reported in computer simulations. LP formation so far has been achieved only for binary mixtures of colloidal charged spheres or ligand-stabilized nano-particles after drying. Using static light scattering, we monitored LP formation and annealing in a binary mixture of buoyant hard sphere approximants (size ratio Γ = 0.77, number or molar fraction of small spheres xS = 0.76) for volume fractions in the fluid-crystal coexistence regions. All samples spontaneously formed MgZn2 type LPs on the time scale of weeks to months via bulk nucleation and growth. Irrespective of the initial suspension volume fractions, the LP volume fraction at coexistence is ΦCOEX = 0.59 which is significantly below the close packing limit ΦMAX = 0.615 and remarkably close to the expectation from simulation. At low volume fractions, crystals anneal to high quality during coarsening which is in line with recent theoretical expectations for the thermodynamic stability of different LP types. At large volume fractions, however, the diffractograms evolve towards a more MgCu2-like appearance which we attribute to the formation of randomly stacked LPs. Such structures are not known from atomic systems.

Coupling between bulk- and surface chemistry in suspensions of charged colloids.

The ionic composition and pair correlations in fluid phases of realistically salt-free charged colloidal sphere suspensions are calculated in the primitive model. We obtain the number densities of all ionic species in suspension, including low-molecular weight microions, and colloidal macroions with acidic surface groups, from a self-consistent solution of a coupled physicochemical set of nonlinear algebraic equations and non-mean-field liquid integral equations. Here, we study suspensions of colloidal spheres with sulfonate or silanol surface groups, suspended in demineralized water that is saturated with carbon dioxide under standard atmosphere. The only input required for our theoretical scheme are the acidic dissociation constants pKa, and effective sphere diameters of all involved ions. Our method allows for an ab initio calculation of colloidal bare and effective charges, at high numerical efficiency.

Charged colloidal model systems under confinement in slit geometry: a new setup for optical microscopic studies.

A new experimental setup for optical microscopic studies of charged colloidal model systems under confinement between two flat walls is presented. The measurement cell consists of optically flat quartz substrates attached to piezo actuators. Those facilitate fast and flexible adjustment of the confining geometry. Optionally, the local cell height can be quantitatively controlled by in situ interferometric measurements. Proper choice of materials guarantees sufficient chemical inertia against contamination with salt ions. For efficient preparation of charged colloidal suspensions under strongly deionized conditions, the cell can be connected to a conventional pump circuit including a mixed bed ion exchanger column. The usefulness of this setup, in particular for investigating the equilibrium phase behavior of colloids at low background salt concentrations, is demonstrated recalling recent experiments.

Crystalline multilayers of charged colloids in soft confinement: experiment versus theory.

We combine real-space experiments and lattice sum calculations to investigate the phase diagram of charged colloidal particles under soft confinement. In the experiments we explore the equilibrium phase diagram of charged colloidal spheres in aqueous suspensions confined between two parallel charged walls at low background salt concentrations. Motivated by the experiments, we perform lattice sum minimizations to predict the crystalline ground state of point-like Yukawa particles which are exposed to a soft confining wall potential. In the multilayered crystalline regime, we obtain good agreement between the experimental and numerical findings: upon increasing the density we recover the sequence [structure: see text].

Colloidal crystallization in the quasi-two-dimensional induced by electrolyte gradients.

We investigated driven crystal formation events in thin layers of sedimented colloidal particles under low salt conditions. Using optical microscopy, we observe particles in a thermodynamically stable colloidal fluid to move radially converging towards cation exchange resin fragments acting as seed particles. When the local particle concentration has become sufficiently large, subsequently crystallization occurs. Brownian dynamics simulations of a 2D system of purely repulsive point-like particles exposed to an attractive potential, yield strikingly similar scenarios, and kinetics of accumulation and micro-structure formation. This offers the possibility of flexibly designing and manufacturing thin colloidal crystals at controlled positions and thus to obtain specific micro-structures not accessible by conventional approaches. We further demonstrate that particle motion is correlated with the existence of a gradient in electrolyte concentration due to the release of electrolyte by the seeds.

Particle characterization using multiple scattering decorrelation methods: hard-sphere model system

Applying static light scattering experiments, we characterize colloidal particles that are used as model hard-sphere systems in experiments investigating their crystallization kinetics. The particles comprise of a compact core of poly(methyl methacrylate) and short polymer hairs grafted onto the surface. We use a contrast variation procedure to determine the refractive index variation within the particles and observe that one component of the binary mixture used as a solvent penetrates the particles and masks completely the small polymer hairs. Making use of the determined refractive index variation, we obtain the average particle radius and its polydispersity from measurements of the particle form factor close to its minimae. The scattered intensity has been corrected carefully for multiple scattering contributions applying dynamic light scattering measurements with multiple scattering decorrelation. We obtain a mean particle radius of &Rmacr;=435+/-4 nm and a polydispersity of sigma=2.5%, a resolution that has not been achieved with light scattering experiments before.

Independent ion migration in suspensions of strongly interacting charged colloidal spheres

We report on systematic measurements of the low-frequency conductivity sigma in aqueous suspensions of highly charged colloidal spheres. Sample preparation in a closed tubing system results in precisely controlled number densities of 10(16) m-3 < or = n < or = 10(19) m-3 (packing fractions of 10(-7) < or = phi < or = 10(-2)) and electrolyte concentrations of 10 < or = c < or = 10(-3) mol l-1. Due to long-range Coulomb repulsion, some of the systems show a pronounced fluid or crystalline order. Under deionized conditions we find sigma to depend linearly on the packing fraction with no detectable influence of the phase transitions. Further, at constant packing fraction sigma increases sublinearly with the increasing number of dissociable surface groups N. As a function of c the conductivity shows pronounced differences depending on the kind of electrolyte used. We propose a simple yet powerful model based on the independent migration of all species present and the additivity of the respective conductivity contributions. It takes account of small ion macro-ion interactions in terms of an effectively transported charge. The model successfully describes our qualitatively complex experimental observations. It further facilitates quantitative estimates of sigma over a wide range of particle and experimental parameters.

Observation of Oriented Close-Packed Lattice Planes in Polycrystalline Hard-Sphere Solids.

We report time-resolved Bragg scattering experiments on solidifying colloidal suspensions of hard spheres. The polar angle-averaged, integrated intensity of the (111) and (311) reflections show a transient, two-step behavior below melting, which depends in a complex way on the volume fraction and is not present for (200) or (220). Detailed analysis of the full two-dimensional scattering pattern reveals intensity maxima of sixfold symmetry close to the position of the (111) and (311) Debye-Scherrer rings. These can be explained assuming oriented crystals with close-packed planes parallel to the container walls. We show that the observed temporal behavior is due to competing homogeneous and heterogeneous nucleation and growth scenarios. Copyright 1998 Academic Press.