Organic monolayers disrupt plastic flow in metals
T Sugihara and A Udupa and K Viswanathan and JM Davis and S Chandrasekar, SCIENCE ADVANCES, 6, eabc8900 (2020).
Adsorbed films often influence mechanical behavior of surfaces, leading to well-known mechanochemical phenomena such as liquid metal embrittlement and environment-assisted cracking. Here, we demonstrate a mechanochemical phenomenon wherein adsorbed long-chain organic monolayers disrupt large-strain plastic deformation in metals. Using high-speed in situ imaging and post facto analysis, we show that the monolayers induce a ductile-to-brittle transition. Sinuous flow, characteristic of ductile metals, gives way to quasi-periodic fracture, typical of brittle materials, with 85% reduction in deformation forces. By independently varying surface energy and molecule chain length via molecular self-assembly, we argue that this "embrittlement" is driven by adsorbate-induced surface stress, as against surface energy reduction. Our observations, backed by modeling and molecular simulations, could provide a basis for explaining diverse mechanochemical phenomena in solids. The results also have implications for manufacturing processes such as machining and comminution, and wear.
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