Motif and fabrication process of II-PSS
To mimic the Q-LL of the ice surface (Fig. 1a), a densely surface-grafted poly(methyl methacrylate) (PGMA) layer was initially fabricated on initiator-functionalized SiO2/Si substrate by surface-initiated Cu(0)-mediated atom transfer radical polymerization (SI-Cu0ATRP, Fig. 1b and Supplementary Fig. 1)28,32-35. The surfaced-grafted PGMA layer on SiO2/Si substrate presented an ultra-smooth polymer matrix surface with a root-mean-square (RMS) roughness of ~ 0.4 nm and thickness of ~ 186.7 nm (Fig. 2a and Supplementary Figs. 2, 3). Then, a solution of perfluoropolyether (PFPE) was spread on the PGMA matrix forming a dynamic liquid layer due to the molecular-level interactions (i.e., dipole-dipole) between PFPE and PGMA31 (Fig. 1b inset). The cross-sectional scanning electron microscope (SEM) image of II-PSS showed a stable coating with thickness of ~ 925 nm on the surface of PGMA matrix (Supplementary Fig. 4). The X-ray photoelectron spectroscopy (XPS) analysis of II-PSS demonstrated the exitance of C (284.8 eV), O (532.7 eV) and F (688.7 eV) elements, while only C and O elements were detected for the PGMA film layer (Supplementary Fig. 5), which further proved the formation of PFPE layer on the PGMA surface.
To verify the interactions between PFPE and PGMA, the interfacial adhesion energy and adhesion force were calculated via molecular dynamics (MD) simulation36,37. Meanwhile, the poly(methyl acrylate) (PMA) with only ester group and poly(methyl methacrylate) (PMMA) with ester and methyl groups (Fig. 2b inset) were selected and modeled with the PFPE for comparison. The results showed that the interfacial adhesion energy between PGMA and PFPE (PGMA-PFPE) was 76.9 kcal·mol−1 which was significantly higher than the two other models with 56.0 kcal·mol−1 (PMA-PFPE) and 58.6 kcal·mol−1 (PMMA-PFPE), respectively (Fig. 2b). In addition, the interfacial adhesion force of the PGMA-PFPE was also the largest and up to 6.6 nN (Fig. 2c and Supplementary Fig. 6). Furthermore, the contribution of the methyl group (-CH3), ether group (C-O-C) and ester group (O-C=O)31 to the interfacial adhesive energy were calculated. According to the results, the dipole-dipole interactions between ether group and -CF2 or -CF3 groups played the major role in the interacted process (~ 4.2 kcal/mol and ~ 4.9 kcal/mol), while the contribution of methyl with -CF2 or -CF3 groups was weaker (~ 1.5 kcal/mol and ~ 1.0 kcal/mol, Fig. 2d and Supplementary Fig. 7), which further theoretically confirmed the robust intermolecular forces of II-PSS
The liquid repellency of the II-PSS was assessed by measuring the contact angles and sliding angles of a wide range of tested liquids, including water and organic liquids. As demonstrated in Fig. 2e, The II-PSS showed the highest water contact angle of 118.2° than blank substrate (36.4°), initiator-functionalized substrate (59.2°) or PGMA (78.2°), meanwhile the II-PSS also presented the lowest sliding angle of 3.8°. In addition, the SiO2/Si substrate coated with the II-PSS showed low sliding angles for liquids with a broad range of surface tensions. For example, the time-lapse images of water (γ = 72.8 mN m−1) and ethanol (γ = 22.1 mN m−1) droplets slid easily off the surface with a tilting angle (TA) of 3° (Fig. 2e and Supplementary Fig. 8). Other organic solvents such as toluene, dimethyl formamide (DMF), diethylene glycol, dimethyl sulfoxide (DMSO), ethylene glycol, and glycerol, underwent slipping motion on the II-PSS by simply tilting the surface, and there were no any residual traces leaving behind (Fig. 2f, Supplementary Fig. 9 and Supplementary Movie 1). Although the contact angles increased with increasing surface tension of the liquids (Fig. 2g), the sliding angles of all the tested liquids were still as low as ~ 5° (Fig. 2h), indicating the excellent liquid repellency of the resultant slippery surface.
To demonstrate the generality of the coating, we prepared the II-PSS on various substrates such as glass, polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polyvinyl chloride (PVC) and aluminum oxide (Al2O3). The water contact angles of II-PSS on different substrates were all increased compared to the blank substrates (Fig. 3a and Supplementary Fig. 10). At the same time, all the II-PSS on different substrates exhibited small water contact angle hysteresis (~ 6.5°) [CAH, difference between the advancing (qadv) and receding (qrec)], which represented less lateral adhesion of the droplets to the surface and thus the low sliding angles (~ 5°) (Fig. 3b). As shown in Fig. 3c, the water droplets could quickly slide off from those II-PSS coated substrates at a tilt angle of 20°, even as short as only 1s on the coated polyethylene surface. Interestingly, a large area of II-PSS coated glass (200 cm2) exhibited high transparency with negligible visibility fading (Fig. 3d insets and Supplementary Fig. 11). Compared to the bare glass (90.1%), the glass coated with II-PSS showed higher optical transparency (94.1%) at the visible light wavelength, which was due to the reduced light scattering through the II-PSS enabled by the replacement of the unwanted solid/air interface with a smoother liquid/air interface (Fig. 3d)38.
Chemical and mechanical stability of II-PSS
The chemical and mechanical stabilities of II-PSS are very important for practical application and thus further investigated. The water contact angles of the liquid droplets of different pH values (from 1 to 13) on II-PSS tended to be stable (~ 114.6°) and the sliding speed changed very slightly (Fig. 4a), as proven by the approximate spherical shape of those dyeing droplets (Fig. 4a insets). The same tendency was obtained to liquid droplets with various salinity (0-7wt.%, Fig. 4b), indicating the excellent chemical stability of the II-PSS. A continuous droplets impacting test was then carried out to assess the durability of the II-PSS towards external mechanical effects39. The water droplets were released continuously on the II-PSS coated glass at a tilt angle of 30° (Supplementary Movie 2), and it was gratifying to see the sliding speed of droplets were almost unchanged between 0-400 drops. Although the sliding speed tended to decrease gradually with the continuously increase of the number of droplets, the sliding property did not disappear (Fig. 4c). Furthermore, when the II-PSS was rotated at 0-7000 rpm/min for an indicated time interval40, the water contact angle changed marginally from 115.3° to 117.9°, and the sliding velocity remained relatively steady at 27.4 mm·s-1, which demonstrated that the lubricating layer remained on the polymer matrix surface (Fig. 4d).
Self-cleaning and anti-fouling properties
It is well acknowledged that the slippery surfaces have great application prospects in the fields of self-cleaning and antifouling41-44. As such, the self-cleaning property of the II-PSS was investigated with four typical liquids that were commonly used in daily life including milk, soy sauce, cooking oil, and cola. The testing samples were tilted to 20°, and all of the tested pollution liquids could quickly slide off the II-PSS coated glass without leaving any residues, which was in clear contrast to the control glass substrate (Fig. 5a, Supplementary Fig. 12 and Supplementary Movie 3).
Subsequently, the anti-fouling properties of II-PSS were examined, and fluorescently labeled bovine serum albumin (BSA) was used as model to test anti-protein adhesion45. The fluorescence microscopy photos showed that there was almost no detectable fluorescence signal from protein on the II-PSS but obvious green fluorescence on the blank surface and PGMA surface (Fig. 5b). Similarly, mussels attach indiscriminately to virtually any surface via adhesive elastomeric foot protein46,47. As expected, the II-PSS could also efficiently prevent the adhesion of mussels (Fig. 5c and Supplementary Fig. 13). In addition, algae are also one of the main biological pollutants in the marine fouling process48. We immersed the samples in a suspension of chlorella and observed few green spots on the fluorescent microscope picture of II-PSS, but massive signals on blank substrate, initiator-functionalized substrate and PGMA matrix, indicating that the II-PSS remained effectively for anti-chlorella adhesion (Fig. 5d).
We finally investigated the long-term marine antifouling behavior of the II-PSS lasting for one month by choosing phaeodactylum tricornutum as a model organism. The samples were immersed in suspension of phaeodactylum tricornutumin for 1, 3, 7 and 30 days, respectively, and then photographed by confocal laser scanning microscope. We found that only a few fluorescent spots appeared on the II-PSS with the increase of time, on the contrary, the amount of algae adhesion on other three kinds of the sample surfaces increased significantly with time (Fig. 6a and Supplementary Fig. 14). In order to observe a more pronounced contrast of the experimental phenomena, one sample was processed into a half-blank and half-II-PSS surface and the same algal adhesion experiment was carried out. As expected, there was a clear dividing line for algal adhesion between the II-PSS coated surface and blank counterpart (Fig. 6b). In addition, the calculation result showed that the adhesion area of algae on the II-PSS was only 0.7% after 30 days (Fig. 6c). The aforementioned results demonstrated that the II-PSS has an excellent durability for practical marine antifouling.