The knowledge of just two parameters characteristic of colloidal systems can help with the understanding of their microstructure and hence offer insight into their stability, rheology and other performance behaviours. The first is the in situ average particle size, which may contain the particle aggregation information, and the second is the volume fraction of the particles. This chapter reviews the emergence of a new structural probe for colloidal liquids in their neat unperturbed state. The technique combines two recent advances in refractometry - an expression for the refractive index of particulate systems as a function of the size and volume concentration of the particles and the availability of digital refractometers which measure the refractive index of concentrated colloids with increased accuracy.
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