Early (pre-DLVO) studies of particle aggregation

The history of colloid science, from its modern foundations in the mid-nineteenth century, has been strongly concerned with studies of the aggregation of colloidal particles. It was Thomas Graham (1861) who defined the word “colloid” (from the Greek word for glue) for those materials which could not pass through membranes, unlike smaller, truly-dissolved materials. Subsequently, Graham (1864), following earlier studies, principally by Selmi and Faraday, described “the power possessed by salts for destroying colloidal solutions”. Although numerous, quantitative studies of particle aggregation were made in the years that followed, in particular, the determination of minimum electrolyte concentrations for the onset of particle aggregation and aggregation rates, no general theoretical framework emerged to account for these quantitative findings until the middle of the twentieth century. It was during and immediately following the Second World War that two sets of authors, Derjaguin and Landau, in Russia, and Verwey and Overbeek, in the Netherlands, independently came up with the theory that is now universally referred to as the DLVO theory of particle interactions and aggregation. All modern developments of the theory of particle aggregation use the DLVO theory as the keystone. However, the DLVO theory itself was based on a large body of experimental data in regard to particle aggregation obtained over the previous hundred years or so. This article is an attempt to review that body of experimental data and to show how this guided the DLVO authors in their thinking.