G. J. Vroege

Convenient preparation methods for magnetic colloids

Abstract We present convenient laboratory-scale preparation methods for maghemite grafted with fatty acids as well as maghemite–silica core–shell colloids.

Direct observation of dipolar chains in ferrofluids in zero field using cryogenic electron microscopy

The particle structure of ferrofluids is studied in situ, by cryogenic electron microscopy, on vitrified films of iron and magnetite dispersions. By means of synthesis of iron colloids with controlled particle size and different types of surfactant, dipolar particle interactions can be varied over a broad range, which significantly influences the ferrofluid particle structure. Our experiments on iron dispersions (in contrast to magnetite dispersions) for the first time demonstrate, in ferrofluids in zero field, a transition with increasing particle size from separate particles to linear chains of particles (Butter K, Bomans P H, Frederik P M, Vroege G J and Philipse A P 2003 Nature Mater. 2 88). These chains, already predicted theoretically by de Gennes and Pincus (de Gennes P G and Pincus P A 1970 Phys. Kondens. Mater. 11 189), very much resemble the fluctuating chains found in simulations of dipolar fluids (Weis J J 1998 Mol. Phys. 93 361, Chantrell R W, Bradbury A, Popplewell J and Charles S W 1982 J. Appl. Phys. 53 2742). Decreasing the range of steric repulsion between particles by employing a thinner surfactant layer is found to change particle structures as well. The dipolar nature of the aggregation is confirmed by the alignment of existing chains and individual particles in the field direction upon vitrification of dispersions in a saturating magnetic field. Frequency-dependent susceptibility measurements indicate that particle structures in truly three-dimensional ferrofluids are qualitatively similar to those in liquid films.

Liquid crystal phase transitions in suspensions of mineral colloids: new life from old roots

A review is given of the field of mineral colloidal liquid crystals: liquid crystal phases formed by individual mineral particles within colloidal suspensions. Starting from their discovery in the 1920s, we discuss developments on the levels of both fundamentals and applications. We conclude by highlighting some promising results from recent years, which may point the way towards future developments.

Isotropic–nematic phase behavior of length-polydisperse hard rods

The isotropic–nematic phase behavior of length-polydisperse hard rods with arbitrary length distributions is calculated. Within a numerical treatment of the polydisperse Onsager model using the Gaussian trial function ansatz we determine the onset of isotropic–nematic phase separation, coming from a dilute isotropic phase and a dense nematic phase. We focus on parent systems whose lengths can be described by either a Schulz or a “fat-tailed” log-normal distribution with appropriate lower and upper cutoff lengths. In both cases, very strong fractionation effects are observed for parent polydispersities larger than roughly 50%. In these regimes, the isotropic and nematic phases are completely dominated by, respectively, the shortest and the longest rods in the system. Moreover, for the log-normal case, we predict triphasic isotropic–nematic–nematic equilibria to occur above a certain threshold polydispersity. By investigating the properties of the coexisting phases across the coexistence region for a partic...

Nematic order of model goethite nanorods in a magnetic field

We explore the nematic order of model goethite nanorods in an external magnetic field within Onsager-Parsons density functional theory. The goethite rods are represented by monodisperse, charged spherocylinders with a permanent magnetic moment along the rod main axis, forcing the particles to align parallel to the magnetic field at low field strength. The intrinsic diamagnetic susceptibility anisometry of the rods is negative, which leads to a preferred perpendicular orientation at higher field strength. It is shown that these competing effects may give rise to intricate phase behavior, including a pronounced stability of biaxial nematic order and the presence of reentrant phase transitions and demixing phenomena.

Uniaxial and biaxial liquid crystal phases in colloidal dispersions of board-like particles

Dispersions of board-like goethite (α-FeOOH) particles with short-range repulsive interaction form a versatile colloidal model system, showing a nematic, smectic A and columnar phase. In high magnetic fields a biaxial nematic phase is induced with the shortest dimension of the particles aligned along the field. Moreover, if particles have a shape almost exactly in between rod-like and plate-like they can spontaneously, without external magnetic field, form biaxial nematic and biaxial smectic A phases, which is in accordance with theoretical predictions. The macroscopic domains were oriented by a magnetic field and their structure was revealed by small-angle X-ray scattering. Our results suggest that biaxial phases can be readily obtained by a proper choice of the particle shape.

Structural transitions of hard-sphere colloids studied by spin-echo small-angle neutron scattering

The structure of hard-sphere colloidal suspensions is measured at different concentrations using the recently developed spin-echo small-angle neutron scattering (SESANS) technique. It is shown that SESANS measures real-space correlations ranging from the size of a single particle for a dilute suspension to several particle diameters for a concentrated suspension, glass and crystalline state.

Influence of polydispersity on the phase behavior of colloidal goethite

The effect of fractionation on the phase behavior of colloidal goethite dispersions with different polydispersities (17%, 35%, and 55% in length) has been studied by small angle x-ray scattering and transmission electron microscopy. All systems show at least nematic and smectic phases. The occurrence of the latter phase at such a high polydispersity is remarkable. It is shown that in the highly polydisperse systems strong fractionation occurs, which is able to reduce the local length polydispersity up to a factor of 2. A columnar phase was only found in the 35% and 55% polydisperse systems. It seems that the columnar phase accommodates the particles that do not fit into the smectic layers and, thus, reduces the length polydispersity within the smectic phase even further. The fact that a columnar phase was not found in the system of lowest polydispersity indicates that the smectic phase is the most stable phase at higher concentrations.

Isotropic-nematic phase separation in asymmetrical rod-plate mixtures

Recent experiments on mixtures of rodlike and platelike colloidal particles have uncovered the phase behavior of strongly asymmetrical rod-plate mixtures. In these mixtures, in which the excluded volume of the platelets is much larger than that of the rods, an extended isotropic (I)–plate-rich nematic (N-)–rod-rich nematic (N+) triphasic equilibrium was found. In this paper, we present a theoretical underpinning for the observed phase behavior starting from the Onsager theory in which higher virial terms are incorporated by rescaling the second virial term using an extension of the Carnahan–Starling excess free energy for hard spheres (Parsons’ method). We find good qualitative agreement between our results and the low concentration part of the experimental phase diagram.

Demixing in binary mixtures of anisometric colloids

An overview is given of the isotropic and nematic phase behaviour in binary mixtures of hard rods or plates with different lengths or diameters within the framework of the Onsager theory. On the basis of Gaussian trial functions the relative importance of different entropic contributions in the demixing of the isotropic and nematic phases is explained for different mixtures. Modifications of this theory are discussed and new results are given for mixtures of plates differing only in diameter or thickness.