mz6b00772_si_001.pdf (1.24 MB)
Stability of Polymer Grafted Nanoparticle Monolayers: Impact of Architecture and Polymer–Substrate Interactions on Dewetting
journal contribution
posted on 2016-11-28, 20:34 authored by Justin Che, Ali Jawaid, Christopher A. Grabowski, Yoon-Jae Yi, Golda Chakkalakal Louis, Subramanian Ramakrishnan, Richard A. VaiaThe
stability of polymer thin films is crucial to a broad range
of technologies, including sensors, energy storage, filtration, and
lithography. Recently, the demonstration of rapid deposition on solid
substrates of ordered monolayers of polymer grafted nanoparticles
(PGN) has increased potential for inks to additively manufacture such
components. Herein, enhanced stability against dewetting of these
self-assembled PGN films (gold nanoparticle functionalized with polystyrene
(AuNP-PS)) is discussed in context to linear polystyrene (PS) analogues
using high throughput surface gradients: surface energy (20–45
mN/m) and temperature (90–160 °C). PGNs exhibit a lower
surface (γp) and interfacial (γsp) energy relative to linear polymers, which results in increased
thermal and energetic stability by 10–25 °C and 5–15
mN/m, respectively. This enhanced wetting–dewetting transition
is qualitatively consistent with the behavior of star macromolecules
and depends on the architecture of the polymer canopy. Increased film
stability through canopy architecture expands the manufacturability
of thin film hybrids and refines postprocessing conditions to maximize
local PGN order.