A key issue in research on ferrofluids (dispersions of magnetic colloids) is the effect of dipolar interactions on their structure and phase behaviour, which is not only important for practical applications but gives fundamental insight in dipolar fluids in general. In 1970, de Gennes and Pincus predicted a Van der Waals-like phase diagram and the presence of linear chains of particles in ferrofluids in zero magnetic field. Despite many experimental studies, no direct evidence of the existence of linear chains of dipoles has been reported in the absence of magnetic field, although simulations clearly show the presence of chain-like structures. Here, we show in situ linear dipolar structures in ferrofluids in zero field, visualized on the particle level by electron cryo-microscopy on thin, vitrified films of organic dispersions of monodisperse metallic iron particles. On systematically increasing the particle size, we find an abrupt transition from separate particles to randomly oriented linear aggregates and branched chains or networks. When vitrified in a permanent magnetic field, these chains align and form thick elongated structures, indicating lateral attraction between parallel dipole chains. These findings show that the experimental model used is well suited to study the structural properties of dipolar particle systems.

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 [1]. These chains, already predicted theoretically by de Gennes and Pincus [2], very much resemble the fluctuating chains found in simulations of dipolar fluids [3,4]. 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 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. 6 Direct observation of dipolar chains in ferrofluids in zero-field using cryogenic electron microscopy This chapter was earlier published as a paper in the special issue on magnetic colloids of the Journal of Physics: Condensed Matter [38]. To preserve the structure of this paper, we chose to present it here in its original shape. Consequently, some textual parts and tables from other chapters are present in this chapter as well.

The dynamic magnetic susceptibility of relatively monodisperse iron ferrofluids was measured from 1 Hz to 100 kHz for different sizes of the iron particles (all with a 7-nm-thick organic surface layer, dispersed in Decalin). In the case of particles with an iron core of 6-nm radius, the orientation of the magnetic dipole moment thermally rotated inside the particles (Néel rotation). In the case of particles with a slightly larger iron core, the orientation of the magnetic dipole moment was blocked inside the particles but could still change by rotational diffusion of the particles themselves (Brownian rotation). With even larger particles (above 7-nm iron core radius), aggregates were formed:  the rotational diffusion rate was lower than that of single particles by more than 1 order of magnitude. This sudden appearance of aggregates above a certain size of the iron particles agrees with previous observations in two dimensions, by cryogenic transmission electron microscopy of ultrathin ferrofluid films. Here, it is found that the threshold for aggregation is practically the same in three dimensions. Moreover, the rotational diffusion rate of the aggregates is seen to increase upon dilution, indicating a decrease in aggregate size. This suggests that a dynamic equilibrium exists between the sticking of particles to each other and unsticking, especially when the particles are sufficiently small so that the sticking energy is not more than a few times the thermal energy.

This paper describes the characterization of dispersions of oleic-acid-coated magnetic iron particles by small-angle neutron and X-ray scattering (SANS and SAXS). Both oxidized and non-oxidized dilute samples were studied by SANS at different contrasts. The non-oxidized samples are found to consist of noninteracting superparamagnetic single dipolar particles, with a lognormal distribution of iron cores, surrounded by a surfactant shell, which is partially penetrated by solvent. This model is supported by SAXS measurements on the same dispersion. Small iron particles are expected to oxidize upon exposure to air. SANS was used to study the effect of this oxidation, both on single particles, as well as on interparticle interactions. It is found that on exposure to air, a nonmagnetic oxide layer is formed around the iron cores, which causes an increase of particle size. In addition, particles are found to aggregate upon oxidation, presumably because the surfactant density on the particle surfaces is decreased.

We study the preparation and properties of metallic iron particles, synthesized by thermal decomposition of Fe(CO) 5 in the presence of a stabilizer. By varying the iron carbonyl/polymer ratio, the particle size can be varied from 2 to 10 nm. Particles are characterized by magnetization measurements, transmission electron microscopy (TEM), small angle X-ray scattering and cryo-TEM. Cryo-TEM pictures show linear structures of particles. From susceptibility measurements, it is seen that particles oxidize fast on exposure to air. r