Critical adsorption and boundary layer structure of 2-butoxyethanol+D[sub 2]O mixtures at a hydrophilic silica surface

Howse, Jonathan R.; Manzanares-Papayanopoulos, Emilio; McLure, Ian A.; Bowers, James; Steitz, Roland; Findenegg, Gerhard H.
April 2002
Journal of Chemical Physics;4/22/2002, Vol. 116 Issue 16, p7177
Academic Journal
Neutron reflectivity experiments have been performed to investigate the adsorption behavior of aqueous solutions of n-2-butoxyethanol (n-C[sub 4]E[sub 1]) and i-2-butoxyethanol (i-C[sub 4]E[sub 1]) in D[sub 2]O against a hydrophilic silica substrate. The measurements were made in the one-phase region near the lower critical solution point of the aqueous systems. At temperatures removed from the lower critical solution temperature, T[sub LCS], evidence for the existence of a microscopically thick (∼40 Å) adsorbed D[sub 2]O-rich layer is presented along with data suggesting that the amphiphile is strongly depleted from the boundary layer. Experiments using a thick “tuning” layer of silica reinforce these observations. Analysis of the data as T→T[sub LCS] reveals that the region beneath the adsorbed D[sub 2]O-rich layer becomes increasingly enriched with D[sub 2]O, and the nature of the composition profile normal to the interface has been considered. Analysis identifies the exponent describing the power-law decay part of the critical adsorption profile appended to the D[sub 2]O-rich region and associates a temperature-dependent correlation length with the critical adsorption profile. Ellipsometric data are presented which complement the neutron reflectivity results. The adsorption behavior of the n-C[sub 4]E[sub 1] and i-C[sub 4]E[sub 1] systems are found to be very similar with the only discernible difference being the magnitude of the adsorption preference of water for the n-C[sub 4]E[sub 1] system in the long-range profile. © 2002 American Institute of Physics.


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