Adsorption of polymers on a brush: Tuning the order of the wetting phase transition.
We develop a computational methodology for the direct measurement of a wetting transition and its order via the effective interface potential. The method also allows to estimate contact angles in the nonwet state and to study adsorption isotherms. The proposed methodology is employed in order to study the wetting behavior of polymers on top of a brush consisting of identical polymers. In the absence of long-range forces, the system shows a sequence of nonwet, wet, and nonwet states as the brush density is increased. Including attractive long-range interactions we can make the polymer liquid wet the bush at all grafting densities, and both first- and second-order wetting transitions are observed. The latter case is limited to a small interval of grafting densities where the melt wets the brush in the absence of long-range interactions. Second-order wetting transitions are preceded by a first-order surface transition from a thin to a thick adsorbed layer. The interval of second-order wetting transitions is limited at low grafting densities by a surface critical end point and at high grafting densities by a tricritical wetting point. Our study highlights the rich wetting behavior that results when competing adsorbent-substrate interactions of different scales are tuned over a broad range.
Macdowell
Luis G
LG
Departamento de Química Física, Facultad de Ciencias Químicas, Universidad Complutense, 28040 Madrid, Spain. luis@ender.quim.ucm.es
Müller
Marcus
M