Effect of hygroscopicity of the metal salt on the formation and air stability of lyotropic liquid crystalline mesophases in hydrated salt-surfactant systems.

It is known that alkali, transition metal and lanthanide salts can form lyotropic liquid crystalline (LLC) mesophases with non-ionic surfactants (such as CiH2i+1(OCH2CH2)jOH, denoted as CiEj). Here we combine several salt systems and show that the percent deliquescence relative humidity (%DRH) value of a salt is the determining parameter in the formation and stability of the mesophases and that the other parameters are secondary and less significant. Accordingly, salts can be divided into 3 categories: Type I salts (such as LiCl, LiBr, LiI, LiNO3, LiClO4, CaCl2, Ca(NO3)2, MgCl2, and some transition metal nitrates) have low %DRH and form stable salt-surfactant LLC mesophases in the presence of a small amount of water, type II salts (such as some sodium and potassium salts) that are moderately hygroscopic form disordered stable mesophases, and type III salts that have high %DRH values, do not form stable LLC mesophases and leach out salt crystals. To illustrate this effect, a large group of salts from alkali and alkaline earth metals were investigated using XRD, POM, FTIR, and Raman techniques. Among the different salts investigated in this study, the LiX (where X is Cl(-), Br(-), I(-), NO3(-), and ClO4(-)) and CaX2 (X is Cl(-), and NO3(-)) salts were more prone to establish LLC mesophases because of their lower %DRH values. The phase behavior with respect to concentration, stability, and thermal behavior of Li(I) systems were investigated further. It is seen that the phase transitions among different anions in the Li(I) systems follow the Hofmeister series.