Advances and challenges in slippery covalently-attached liquid surfaces

Over the past decade, a new class of slippery, anti-adhesive surfaces known as slippery covalently-attached liquid surfaces (SCALS) has emerged, characterized by low values of contact angle hysteresis (CAH, less than 5°) with water and most solvents. Despite their nanoscale thickness (1 to 5 nm), SCALS exhibit behavior similar to lubricant-infused surfaces, including high droplet mobility and the ability to prevent icing, scaling, and fouling. To date, SCALS have primarily been obtained using grafted polydimethylsiloxane (PDMS), though there are also examples of polyethylene oxide (PEO), perfluorinated polyether (PFPE), and short-chain alkane SCALS. Importantly, the precise physico-chemical characteristics that enable ultra-low CAH are unknown, making rational design of these systems impossible. In this review, we conduct a quantitative and comparative analysis of reported values of CAH, molecular weight, grafting density, and layer thickness for a range of SCALS. We find that CAH does not scale monotonically with any reported parameter; instead, the CAH minimum is found at intermediate values. For PDMS, optimal behavior is observed at advancing contact angle of 106°, molecular weight between 2 and 10 kg mol-1, and grafting density of around 0.5 nm-2. CAH on SCALS is lowest for layers created from end-grafted chains and increases with the number of binding sites, and can generally be improved by increasing the chemical homogeneity of the surface through the capping of residual silanols. We review the existing literature on SCALS, including both synthetic and functional aspects of current preparative methods. The properties of reported SCALS are quantitatively analyzed, revealing trends in the existing data and highlighting areas for future experimental study.