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We present a versatile one-pot synthesis method for creating surface-anchored orthogonal gradient networks using a small bi-functional gelator, 4-azidosulfonylphenethyltrimethoxysilane (4-ASPTMS). The sulfonyl azide (SAz) group of 4-ASPTMS is UV (≤254 nm) and thermally active (≥100 °C) and, thus, enables us to vary the cross-link density in orthogonal directions by controlling the activation of SAz groups via UV and temperature means. We deposit a thin layer (∼200 nm) of a mixture comprising ∼90% precursor polymer and ∼10% 4-ASPTMS in a silicon wafer. Upon UV irradiation or annealing the layers, SAz releases nitrogen by forming singlet and triplet nitrenes that concurrently react with any C–H bond in the vicinity leading to sulfonamide cross-links. Condensation among trimethoxy groups in the bulk connects 4-ASPTMS units and completes the cross-linking. Simultaneously, 4-ASPTMS near the substrate reacts with surface-bound –OH motifs that anchor the cross-linked polymer chains to the substrate. We demonstrate the generation of orthogonal gradient network coatings exhibiting cross-link density (or stiffness) gradients in orthogonal directions using such a simple process. 

This paper demonstrates that air‐stable radicals enhance the stability of triboelectric charge on surfaces. While charge on surfaces is often undesirable (e.g., static discharge), improved charge retention can benefit specific applications such as air filtration. Here, it is shown that self‐assembled monolayers (SAMs) containing air‐stable radicals, 2,2,6,6‐tetramethylpiperidin‐1‐yl)oxidanyl (TEMPO), hold the charge longer than those without TEMPO. Charging and retention are monitored by Kelvin Probe Force Microscopy (KPFM) as a function of time. Without the radicals on the surface, charge retention increases with the water contact angle (hydrophobicity), consistent with the understanding that surface water molecules can accelerate charge dissipation. Yet, the most prolonged charge retention is observed in surfaces treated with TEMPO, which are more hydrophilic than untreated control surfaces. The charge retention decreases with reducing radical density by etching the TEMPO‐silane with tetrabutylammonium fluoride (TBAF) or scavenging the radicals with ascorbic acid. These results suggest a pathway toward increasing the lifetime of triboelectric charges, which may enhance air filtration, improve tribocharging for patterning charges on surfaces, or boost triboelectric energy harvesting.