Aggregation and Microstructure in Aqueous Solutions of the Nonionic Surfactant C12E8.

Mixtures of water and of the nonionic surfactant C12E8 (octaoxyethyleneglycol monododecylether) have been investigated by time-resolved fluorescence quenching (TRFQ) and transmission electron microscopy at cryogenic temperature (cryo-TEM) to obtain information on the size and shape of the surfactant aggregates and on the microstructure of the mixtures. The studies were performed at surfactant contents and temperatures where the micelles grew significantly and also where the systems undergo phase transitions from micellar-to-cubic upon increasing surfactant content or decreasing temperature and from cubic-to-hexagonal-to-micellar upon increasing temperature. No rapid change or discontinuity was observed in the variation of the aggregation number with the surfactant content or temperature upon crossing the micellar-to-cubic phase boundary nor at the approach of the hexagonal phase from the cubic phase. The results confirmed that the cubic phase consists of spheroidal micelles forming a three-dimensional array. The aggregation numbers at high surfactant content or temperature can be much larger than that of the minimum spherical micelle for a surfactant with a dodecyl chain, suggesting that the micelles should be anisotropic. However, cryo-TEM showed that in the micellar phase the micelles are always spheroidal. These apparently inconsistent results are explained in terms of a partial mixing of the surfactant dodecyl chains and octaoxyethylene head groups which allows for spheroidal micelles of aggregation number much larger than for a surfactant with a dodecyl chain. The results show extensive exchange of material at 40°C, taking place most likely via temporary merging of micelles in micelle clusters then present in the system.