Linked influence of pH and cations on fatty-acid monolayer integrity related to high-quality Langmuir-Blodgett films

This study shows the connection between the morphological structure of transferred films and the chemical composition of the monolayer before transfer. The stability of a behenic acid monolayer depends on the linked influence of the type of cation and of the pH value in the aqueous subphase. The stability of the monolayer is assessed by the expansion of the solid-packed state and by the relaxation time. Its integrity is characterized by the number of crystal defects which appear in transferred Langmuir-Blodgett (LB) films as seen through Nomarski microscope observations. Both stability and integrity are greatly improved when Cd²⁺ or Mn²⁺are added to the subphase at pH 5.75 and 6 respectively. In these conditions, the transfer is very efficient and the LB films thus obtained are of very high quality. The pH values of the subphase at which the molecules of behenic acid are transformed into bivalent salts differ significantly according to the nature of the cation involved. Comparing infrared spectra of the LB films, it appeared that the relative amount of acid/salt found in the monolayer was practically the same with a subphase containing either Cd²⁺ at pH 5.75 or Mn²⁺ at pH 6. This suggests that the ratio of acidic and salt forms would be a key parameter for obtaining high-quality LB films.