Effect of Counterion Species on Colloidal Crystal

The effect of counterion species on the colloidal crystal structure in a dispersion was carefully investigated as a function of the degree of neutralization (alpha) by the ultra-small-angle X-ray scattering technique. The nearest neighbor interparticle distance (2D(exp)) first increased with decreasing alpha, and then decreased after passing through the maximum. This behavior was confirmed for K(+), Li(+), Ca(2+), TMA(+) (tetramethylammonium) as a counterion, and Na(+) in our previous report (Harada, T.; Matsuoka, H.; Ikeda, T.; Yamaoka, H. Langmuir 2000, 16, 1612). However, the alpha value of the maximum position (alpha(max)) largely depended on the counterion species, and it was in the order K(+) < Na(+) < TMA(+) approximately Li(+). This behavior was well characterized by the specific features of each ion: the alpha(max) map could be well superimposed in the Stokes radius-crystal ion radius relationship of counterions. The alpha(max) dependence on Stokes radius was very similar to that of the B coefficient by Jones and Dole except in the case of Ca(2+). In principle, the smaller the value for B, the smaller alpha(max), indicating that a water structure breaker such as K(+) can more easily destroy the colloidal crystal structure. In other words, the effect of the counterion species on colloidal crystal stability follows the Hofmeister series. Including Ca(2+), the relationship was linear for the alpha(max) values plotted as a function of the limiting equivalent conductivity of small ions. A counterion with larger conductivity would be a stronger breaker for the colloidal crystal structure.