École Supérieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI), ParisTech, PSL Research University, Sciences et Ingénierie de la Matière Molle (SIMM), CNRS UMR 7615, 10 rue Vauquelin, F-75231 Paris cedex 05, France.
Soft Matter. 2017 Feb 8;13(6):1299-1305. doi: 10.1039/c6sm01846g.
Molecular interactions in thin liquid films, such as the disjoining pressure, are involved in interfacial phenomena such as emulsion and foam stabilization. In this article we show that through light stimulation we can control remotely the disjoining pressure in a thin liquid film stabilized by a photosurfactant. We stabilize a horizontal thin liquid film using a cationic photosurfactant, AzoTAB, bearing an azobenzene moiety on the hydrophobic tail which can switch from a trans to a cis conformation upon light stimulation. As the film is illuminated at specific wavelengths the AzoTAB molecules switch continuously their conformation and consequently their interface affinity. The main consequence of stimulating the film with light is increasing the ratio of cis in the film. This provokes a desorption flux, and an increase in the concentration of free surfactants, as the CMC of the cis isomer is higher than that of the trans isomer. Therefore the electrostatic repulsion between the surfactant layers that stabilize the film decreases, inducing an instability in the film thickness. For films with a thickness between 20 nm and 60 nm, we observe the formation of spherical caps up to 100 μm wide, whose shape is controlled by the competition between surface tension and disjoining pressure. The motion of these caps in the film is restrained by the surface viscosity of the surfactant layers. In addition, for thicknesses below 40 nm and depending on light intensity, we can observe flat stratified islands up to 100 μm wide, with thickness steps corresponding to the size of a surfactant micelle. We suggest that this second instability is due to the oscillation of the disjoining pressure isotherm under light.
薄液膜中的分子相互作用,如离隙压力,涉及到界面现象,如乳液和泡沫的稳定。在本文中,我们展示了通过光刺激,我们可以远程控制由光活性表面活性剂稳定的薄液膜中的离隙压力。我们使用带有偶氮苯部分的阳离子光活性表面活性剂 AzoTAB 来稳定水平薄液膜,该部分可以在光刺激下从反式构象切换到顺式构象。当膜在特定波长下被照射时,AzoTAB 分子会连续地切换它们的构象,从而改变它们在界面上的亲和力。用光刺激膜的主要后果是增加膜中顺式的比例。这会引起解吸通量的增加,以及游离表面活性剂浓度的增加,因为顺式的 CMC 高于反式的 CMC。因此,稳定膜的表面活性剂层之间的静电排斥力减小,导致膜厚度不稳定。对于厚度在 20nm 到 60nm 之间的膜,我们观察到直径可达 100μm 的球形帽的形成,其形状由表面张力和离隙压力之间的竞争决定。这些帽在膜中的运动受到表面活性剂层的表面粘度的限制。此外,对于厚度低于 40nm 且取决于光强度,我们可以观察到宽度可达 100μm 的平坦分层岛,其厚度台阶对应于表面活性剂胶束的大小。我们认为这种第二个不稳定性是由于离隙压力等温线在光下的振荡引起的。