Surfactant Self-Assembly Structures at Interfaces, in Polymer Solutions, and in Bulk: Micellar Size and Connectivity

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Abstract
It was G. S. Hartley who made the pioneering contributions to our understanding of the physical nature of globular micelles (1,2). He realized inter alia the liquid-like nature of the hydrocarbon interior of the micelle and the minimal contact between the solvent water and the surfactant hydrocarbon chains as the main driving force for the association. As illustrated in Figure 1, he pictured the interior of a micelle as essentially “a droplet of liquid paraffin” with the chains in “as near as can be done, a completely chaotic arrangement.” He also argued strongly against some of his contemporaries drawing pictures with radially oriented straight alkyl chains (1): “The symmetrical ‘asterisk’ form so frequently drawn would imply a high degree of organisation and a density of great magnitude in the centre and of less magnitude near the circumference. It has no physical basis and is drawn of no other reason than that the human mind is an organising instrument and finds unorganised processes uncongenial.” Figure 1 Schematic of spherical and elongated micelles, and conformations of surfactant molecules therein, as proposed by Hartley. (From Ref. 2, used with permission; copyright Kolloid-Z, 1940.)

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