Molecular origin of slippery behaviour in tethered liquid layers

Fuente: arXiv
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Main Authors: Rasera, Fabio, Gresham, Isaac J., Tinti, Antonio, Neto, Chiara, Giacomello, Alberto
Format: Preprint
Published: 2024
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author Rasera, Fabio
Gresham, Isaac J.
Tinti, Antonio
Neto, Chiara
Giacomello, Alberto
author_facet Rasera, Fabio
Gresham, Isaac J.
Tinti, Antonio
Neto, Chiara
Giacomello, Alberto
contents Slippery covalently attached liquid surfaces (SCALS) are a family of nanothin polymer layers with remarkably low static droplet friction, characterised by a low contact angle hysteresis (CAH$< 5 °$), which makes them ideally suited to self-cleaning, water harvesting, and anti-fouling applications. Recently, a Goldilocks zone of lowest CAH has been identified for polydimethyl siloxane (PDMS) SCALS of intermediate thickness (3.5 nm), yet, molecular-level insights are missing to reveal the underlying physical mechanism of this elusive, slippery optimum. In this work, the agreement between coarse-grained molecular dynamics simulations and atomic force microscopy data shows that nanoscale defects, as well as deformation for thicker layers, are key to explaining the existence of this `just right' regime. At low thickness values, insufficient substrate coverage gives rise to chemical patchiness; at large thickness values, two features appear: 1) a waviness forms on the surface of the liquid layer due to a previously overlooked lateral microphase separation occurring in polydisperse brushes, and 2) layer deformation due to the contact line is larger than in thinner layers. The most pronounced slippery behaviour occurs for smooth PDMS layers that do not exhibit nanoscale waviness. The converging insights from molecular simulations, experiments, and a contact angle hysteresis theory provide design guidelines for tethered polymer layers with ultra-low contact angle hysteresis.
format Preprint
id arxiv_https___arxiv_org_abs_2410_00815
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Molecular origin of slippery behaviour in tethered liquid layers
Rasera, Fabio
Gresham, Isaac J.
Tinti, Antonio
Neto, Chiara
Giacomello, Alberto
Soft Condensed Matter
Slippery covalently attached liquid surfaces (SCALS) are a family of nanothin polymer layers with remarkably low static droplet friction, characterised by a low contact angle hysteresis (CAH$< 5 °$), which makes them ideally suited to self-cleaning, water harvesting, and anti-fouling applications. Recently, a Goldilocks zone of lowest CAH has been identified for polydimethyl siloxane (PDMS) SCALS of intermediate thickness (3.5 nm), yet, molecular-level insights are missing to reveal the underlying physical mechanism of this elusive, slippery optimum. In this work, the agreement between coarse-grained molecular dynamics simulations and atomic force microscopy data shows that nanoscale defects, as well as deformation for thicker layers, are key to explaining the existence of this `just right' regime. At low thickness values, insufficient substrate coverage gives rise to chemical patchiness; at large thickness values, two features appear: 1) a waviness forms on the surface of the liquid layer due to a previously overlooked lateral microphase separation occurring in polydisperse brushes, and 2) layer deformation due to the contact line is larger than in thinner layers. The most pronounced slippery behaviour occurs for smooth PDMS layers that do not exhibit nanoscale waviness. The converging insights from molecular simulations, experiments, and a contact angle hysteresis theory provide design guidelines for tethered polymer layers with ultra-low contact angle hysteresis.
title Molecular origin of slippery behaviour in tethered liquid layers
topic Soft Condensed Matter
url https://arxiv.org/abs/2410.00815