Self-replenishing ability of cross-linked low surface energy polymer films investigated by a complementary experimental-simulation approach

Abstract

Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication Citation for published version (APA):Esteves, A. C. C., Lyakhova, K., Riel, van, J. M., Ven, van der, L. G. J., Benthem, van, R. A. T. M., & With, de, G. (2014). Self-replenishing ability of cross-linked low surface energy polymer films investigated by a complementary experimental-simulation approach. Journal of Chemical Physics, 140, 1-9. [124902]. DOI: 10.1063/1.4868989 General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Nowadays, many self-healing strategies are available for recovering mechanical damage of bulk polymeric materials. The recovery of surface-dependent functionalities on polymer films is, however, equally important and has been less investigated. In this work we study the ability of low surface energy cross-linked poly(ester urethane) networks containing perfluorinated dangling chains to self-replenish their surface, after being submitted to repeated surface damage. For this purpose we used a combined experimental-simulation approach. Experimentally, the cross-linked films were intentionally damaged by cryo-microtoming to remove top layers and create new surfaces which were characterized by water Contact Angle measurements and X-Ray Photoelectron Spectroscopy. The same systems were simultaneously represented by a Dissipative Particles Dynamics simulation method, where the damage was modeled by removing the top film layers in the simulation box and replacing it by new "air" beads. The influence of different experimental parameters, such as the concentration of the low surface energy component and the molecular m...

Self‐Healing Functional Surfaces

“…The simulations revealed the formation of highly dynamic fluorinated clusters in the bulk, fluctuating considerably in size, and the existence of a depletion zone depleted from dangling ends, just beneath the first air–polymer interface formed. Both experiments and simulations coherently showed that these crosslinked films can self‐replenish their surface chemical composition multiple times ( Figure a). The simulations also showed the reformation of the depletion zone (estimated with a thickness of ≈5 nm) and the presence of new fluorinated clusters in the bulk of the polymer film on the replenished systems (Figure bA–C).…”

“…However, in the experimental approach a full recovery of the F/C atomic ratio was observed for the damaged and replenished films . It is well known that the F/C atomic ratio determined by XPS on soft polymer films may be affected by different error sources, such as burning and smearing of material from the surface by the X‐ray beam during analyses or interference by contamination and roughness developed on the damaged surfaces . Hence, this is a good example were the damage of the surface and the characterization method strongly influence the values estimated for the SHE.…”

“…From the simulations, no particular trend was observed for the SHE with the variation of the length of the polymer spacer in the dangling ends; all films recovered up to 75–80% of their initial F/C atomic ratio. However, in the experimental approach a full recovery of the F/C atomic ratio was observed for the damaged and replenished films . It is well known that the F/C atomic ratio determined by XPS on soft polymer films may be affected by different error sources, such as burning and smearing of material from the surface by the X‐ray beam during analyses or interference by contamination and roughness developed on the damaged surfaces .…”

“…The self‐replenishing mechanism on hydrophobic polymers was further studied by a combined experimental‐simulation approach running in a parallel and loop‐feeding process . For the experimental study, well‐defined crosslinked PU matrices were designed using branched polycaprolactone polyesters and a triisocyanate crosslinker.…”

“…Taking the model hydrophobic self‐replenishing PU system mentioned above as example, the SHE was estimated from both the experimental and simulation approaches. From the simulations, no particular trend was observed for the SHE with the variation of the length of the polymer spacer in the dangling ends; all films recovered up to 75–80% of their initial F/C atomic ratio.…”