The aggregation behavior of one azine and three triphenylmethane cationic dyes in dispersions of reduced-charge montmorillonites (RCMs) was investigated. The extent and types of dye aggregation were monitored using visible spectroscopy. Similar relationships between dye aggregation and layer charge were observed, independent of the structure of the dye cations. High charge-density surfaces induced the formation of H-aggregates, with a face-to-face association between the dye cations that then absorb light at relatively lower wavelengths. Moderate reductions in layer charge were reflected in the lowering of the H-aggregation in favor of monomers, dimers and less densely-packed J-aggregates, absorbing light at higher wavelengths. Dye spectra in the presence of the lowest-charge RCMs resembled those of dilute dye solutions, indicating the absence of dye aggregation of any type in this case. The relationship between dye spectral changes and layer-charge densities of smectites is a general phenomenon which can potentially be used to estimate the layer charge of smectites. However, applying this method to triphenylmethane dyes, which have structurally more complicated cations, may reduce the sensitivity of the probe.

Theories concerning the optical properties of cationic dyes adsorbed on clay surfaces are analysed in detail. An investigation of the aggregation of methylene blue (MB) in montmorillonite dispersions is conducted using visible (VIS) spectroscopy. The effects of the dye/ clay ratio and of the swelling properties of the montmorillonite substrate on dye aggregation are compared in terms of the effect of clay layer charge. The observed influence on dye aggregation was almost negligible for both swelling and dye loading. The layer charge of the silicate determines the extent and the type of dye aggregation in freshly prepared MB/montmorillonite dispersions. Observed spectral changes with time indicate a rearrangement and redistribution of dye H-aggregates (band close to 570 nm) to monomers (660 nm), dimers (605 nm) and J-aggregates (760 nm). Dye aggregates are probably already formed during dye cation migration in the vicinity of clay colloid particles. The extent and the type of initially formed species are probably affected by the electric double layer of clay layers. After reaching the clay surface, dye cation assemblies are rearranged and decompose as described above. Reaching chemical equilibrium, dye cations adjust the distribution of the layer charge, in order that each cation could balance the charge due to one unequivalent substitution.