Durable hydrophobic materials have attracted considerable interest in the last century. Currently, the most popular strategy to achieve hydrophobic coating durability is through the combination of a perfluoro-compound with a mechanically robust matrix to form a composite for coating protection. The matrix structure is typically large (thicker than 10 μm), difficult to scale to arbitrary materials, and incompatible with applications requiring nanoscale thickness such as heat transfer, water harvesting, and desalination. Here, we demonstrate durable hydrophobicity and superhydrophobicity with nanoscale-thick, perfluorinated compound-free polydimethylsiloxane vitrimers that are self-healing due to the exchange of network strands. The polydimethylsiloxane vitrimer thin film maintains excellent hydrophobicity and optical transparency after scratching, cutting, and indenting. We show that the polydimethylsiloxane vitrimer thin film can be deposited through scalable dip-coating on a variety of substrates. In contrast to previous work achieving thick durable hydrophobic coatings by passively stacking protective structures, this work presents a pathway to achieving ultra-thin (thinner than 100 nm) durable hydrophobic films.

Dynamic networks which undergo topology conserving exchange reactions, sometimes called vitrimers, show properties intermediate to thermosets and thermoplastics. The dynamic nature of the networks results in complex rheological properties and has attracted much attention in the past decade for self-healing, malleable and recyclable polymers. Here, we investigate a series of precise, high crosslink density telechelic ethylene vitrimers as a function of temperature and crosslink density. The networks show a rubbery plateau at high frequencies and a terminal flow regime at lower frequencies. With increasing crosslink density, the rubbery plateau modulus shows a monotonic increase and the terminal flow shifts to lower frequencies. The plateau modulus at high frequency increases as a function of temperature, as expected for a conserved network topology. When plotted against inverse temperature, the zero shear viscosities show a characteristic Arrhenius behavior, and the activation energy monotonically increases with crosslink density. Crossover frequency and shift factors (from time temperature superposition) also show Arrhenius behavior with activation energies in good agreement with those determined from zero shear viscosity. A positive deviation from this Arrhenius trend is observed beginning as high as 100 K above the glass transition temperature for C₆ and C₈ networks. Further investigations of such networks are critical for the development of sustainable and recyclable replacements for commercial plastics.