Adsorption from alkane+perfluoroalkane mixtures at fluorophobic and fluorophilic surfaces. II. Crossover from critical adsorption to complete wetting.

Using neutron reflectometry, adsorption from an equimolar mixture of hexane + perfluorohexane to a fluorophobic, octadecyl-coated, silicon substrate has been investigated as a function of temperature in the one-phase region upon approach to liquid-liquid coexistence. The composition of the investigated mixture, x(F) = 0.50, is well removed from the critical composition of x(F) = 0.36, where x(F) is the perfluorohexane mole fraction. To aid the modeling, mixtures with three different neutron refractive index contrasts have been used: namely, mixtures of C(6)H(14) + C(6)F(14) (H-F), C(6)D(14) + C(6)F(14) (D-F), and a mixture of C(6)H(14) + C(6)D(14) + C(6)F(14) which has been adjusted to have the same refractive index as silicon (CMSi). For all three contrasts, the principal features of the composition profile normal to the interface follow similar trends as the temperature T is reduced towards T(0), the coexistence temperature. These features consist of: (i) a hexane-rich primary adsorption layer appended to the octadecyl coupled layer. This primary layer is 22 +/- 5 A thick and becomes increasingly enriched in hexane as T(0) is approached. (ii) A tail that decays exponentially towards the bulk composition with a characteristic decay length zeta. As T(0) is approached, zeta increases. The scattering length density profiles have been converted to volume fraction profiles and the surface excess of hexane Gamma has been determined as a function of temperature for all three contrasts. As T(0) is approached Gamma increases, and its behavior can be represented using the scaling law Gamma approximately |T - T(0)|(-m). The resulting values of m are 0.71 +/- 0.09, 0.68 +/- 0.04, and 0.68 +/- 0.06 for the D-F, H-F, and CMSi contrasts, respectively. The behavior of Gamma with temperature does not adhere to the Gamma approximately |T - T(0)|(-1/3) law expected for complete wetting in systems with van der Waals interactions nor does it correspond to Gamma approximately |T - T(c)|(-0.305) expected for critical adsorption. The magnitude of the exponent m indicates that the adsorption resides in the crossover region between critical adsorption and complete wetting.