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Cation-induced monolayer collapse at lower surface pressure follows specific headgroup percolation

Kaushik Das, Bijay Kumar Sah, and Sarathi Kundu^*

Soft Nano Laboratory, Physical Sciences Division, Institute of Advanced Study in Science and Technology, Vigyan Path, Paschim Boragaon, Garchuk, Guwahati, Assam 781035, India

^*Corresponding author: sarathi.kundu@gmail.com

Phys. Rev. E 95, 022804 – Published 13 February, 2017

DOI: https://doi.org/10.1103/PhysRevE.95.022804

Abstract

A Langmuir monolayer can be considered as a two-dimensional (2D) sheet at higher surface pressure which structurally deform with mechanical compression depending upon the elastic nature of the monolayer. The deformed structures formed after a certain elastic limit are called collapsed structures. To explore monolayer collapses at lower surface pressure and to see the effect of ions on such monolayer collapses, out-of-plane structures and in-plane morphologies of stearic acid Langmuir monolayers have been studied both at lower (≈6.8) and higher (≈9.5) subphase $p H$ in the presence of $M g^{2 +}, C a^{2 +}, Z n^{2 +}, C d^{2 +}$ , and $B a^{2 +}$ ions. At lower subphase $p H$ and in the presence of all cations, the stearic acid monolayer remains as a monolayer before collapse, which generally takes place at higher surface pressure $(π_{c} > 50 mN / m)$ . However, at higher subphase $p H$ , structural changes of stearic acid monolayers occur at relatively lower surface pressure depending upon the specific dissolved ions. Among the same group elements of $M g^{2 +}, C a^{2 +}$ , and $B a^{2 +}$ , only for $B a^{2 +}$ ions does monolayer to multilayer transition take place from a much lower surface pressure of the monolayer, remaining, however, as a monolayer for $M g^{2 +}$ and $C a^{2 +}$ ions. For another same group elements of $Z n^{2 +}$ and $C d^{2 +}$ ions, a less covered bilayer structure forms on top of the monolayer structure at lower surface pressure, which is evidenced from both x-ray reflectometry and atomic force microscopy. Fourier transform infrared spectroscopy confirms the presence of two coexisting conformations formed by the two different metal-headgroup coordinations and the monolayer to trilayer or multilayer transformation takes place when the coverage ratio of the two molecular conformations changes from the critical value $(p_{c})$ of $\approx 0.66$ . Such ion-specific monolayer collapses are correlated with the 2D lattice percolation model.

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Cation-induced monolayer collapse at lower surface pressure follows specific headgroup percolation

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