Stability of the parallel layer during alkane spreading and the domain structures of the standing-up layer

The spreading of liquid alkanes over surfaces plays an important role in applications such as lubrication, painting, and printing. To make significant advances in these fields, it is essential to increase our understanding of the interactions between alkanes and surfaces. Long-chain alkanes form two typical adsorption structures on a surface--the parallel phase and the standing-up phase. The most thermodynamically stable structure is the parallel phase, in which the alkane molecules lie flat on the surface. If the temperature is slightly below the bulk melting point, then alkanes form a thermodynamically stable standing-up phase on top of an existing parallel layer. At lower temperatures, the standing-up phase becomes metastable. Using atomic force microscopy, we have found that the standing-up alkane layer consists of multiple domains, indicating that the standing-up layer forms through a multinucleation process during the liquid-solid transition on the surface. If, however, the temperature is above the melting point, then we have found that the standing-up layer shrinks to a droplet and leaves a residue on its original position. During the spreading of an alkane droplet, the parallel layer forms on the substrate surface surrounding the droplet by adsorption from the vapor, which precedes the arrival of the liquid. There has been uncertainty, however, as to whether the parallel layer moves with the liquid alkane or remains stationary during spreading. In this study, we used the residue left on the parallel layer as a landmark to monitor the movement of the parallel layer during the spreading of an alkane droplet. Using this landmark, we found that the parallel layer remained stationary on the substrate, indicating that the liquid alkane spreads on a stationary parallel layer surface. Therefore, this study reveals that the surface properties of the parallel layer--not the surface properties of the substrate--control the spreading and wetting of a liquid alkane.