Applications of freeze-fracture replication to problems in materials and colloid science

Understanding the relationship between the molecular structure and the macroscopic properties of polymer solutions and gels, oil‐water‐surfactant emulsions, lyotropic and thermotropic liquid crystals, colloidal dispersions, detergents, and other such “microstructured fluids” is essential to the optimal use of these commercially important materials. Modern rapid‐freezing methods followed by freeze‐fracture replication techniques are ideally suited to allow the direct visualization of the three‐dimensional structure of the particles or units that make up the dispersion, while simultaneously revealing their orientation and distribution with molecular resolution. This paper reviews the necessary experimental conditions required to successfully exploit the freeze‐fracture technique as it applies to microstructured fluid systems. The benefits and limitations of structural studies by freeze‐fracture techniques as opposed to the more commonly used light, X‐ray, and neutron‐scattering methods are discussed. Freeze‐fracture replicas can also be imaged by scanning tunneling microscopy to reveal directly three‐dimensional fracture contours with improved resolution.