Due to the intimate contact at the solid–liquid interface, a water drop in the Wenzel state has a higher contact angle hysteresis and will adhere very efficiently to the substrate in spite of a large static con- tact angle, which is referred to as “sticky” superhydrophobicity. In our case, although the static contact angles for the treated cotton fabrics were all in the range between 151◦ and 157◦, the contact angle hysteresis varied with the number of PAH/SiO2 layer assembled (Fig. 7). For the cotton fabrics assembled with 1 or 3 layers of PAH/SiO2 , the contact angle hysteresis was larger than 45◦ , and the fabric surface is sticky. However, for the fabric treated with 5 or 7 layers of PAH/SiO2, the contact angle hysteresis decreased to less than 10◦ , leading to a “slippery” superhydrophobic surface. The significant decrease in contact angle hysteresis can be attributed to the reduced contribution from the fully wetted Wenzel state.
The force required to move the water drops on the surface is dependent on the contact angle hysteresis [37], F ≈ lv (cos R − cos A) W, where lv is the interfacial tension of the water at the water–air interface, W is the width of the wetted area perpendicular to the movement direction, and A and R are the advancing and receding contact angle, respectively. According to this equation, the values of F normalized with respect to W can be calculated, and the results are shown in Fig. 7. For the cotton fabrics assembled with 1 and 3 layers of PAH/SiO2, the force was 59.3 and 39.1dyn/cm, respectively. When the number of PAH/SiO2 layers was increased to 5 and 7, the force decreased dramatically to 3.1 and 1.3 dyn/cm, respectively. This suggests that it requires only about one-thirteenth of the force, 3.1dyn/cm vs. 39.1dyn/cm, to move a water drop on the fabric assembled with 5 layers of PAH/SiO2 compared to that with 3 layers of PAH/SiO2. It should be pointed out that for the fabric assembled with 5 or 7 layers of PAH/SiO2, the sliding angles were hard to measure because the water drops rolled easily on the fabric surface when the fabric was just gently moved horizontally.
In an attempt to investigate the buoyancy of the superhydrophobic cotton fabrics, we made a miniature boat by using the superhydrophobic fabric assembled with (PAH/SiO2)5 multilayers, and loaded the boat with heavy rubber (density 1.7gcm−3). The volume of the boat was 8.0 cm3 . According to Archimedes’ principle, the loading capacity of this boat on water surface should be 8.0 g. However, we found that the maximum loading capacity for this boat was 11.6 or 12.2 g if the boat weight is included. This suggests that besides the buoyancy force associated with the boat volume of 8.0 cm3 , there is an extra buoyancy force to support the extra load- ing of 4.2 g. Fig. 8 shows the floating behavior of a superhydrophobic fabric boat with a maximum loading. As can be seen, the boat still floated even when its upper edges were below the water surface, which can be ascribed to the extremely low surface energy of the fabric. Therefore, one contribution to the extra buoyancy force is the surface tension force related to the upper perimeter of the boat. Another contribution to the extra buoyancy force comes from the plastron effect [38,39]. The trapped air film surrounding the fabric outer surface provides additional displaced volume of water, and thus extra buoyancy force.
For practical applications, the durability of the superhydrophobic surface is important. In our study, the affinity between the (PAH/SiO2 )5 multilayers and the cotton fiber was tested by immersing the fabric into a sonication bath containing ethanol, which can completely wet the superhydrophobic fabric. After continuous sonication for 1 h, no significant changes in the contact angles were found. In addition, the wash durability test revealed that the contact angle hysteresis of the cotton fabric assembled with (PAH/SiO2)5 multilayers still remained lower than 10◦ after 10 cycles of home laundering, and the static contact angle remained above 150◦ even after 30 cycles (Fig. 9).