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.