Grafted Crystalline Poly‐Perfluoroacrylate Structures for Superhydrophobic and Oleophobic Functional Coatings

Coclite, Anna Maria; Shi, Yujun; Gleason, Karen K.

doi:10.1002/adma.201200682

Cited by 77 publications

(80 citation statements)

References 25 publications

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“…[36][37][38] While copolymerization helps by improving the mechanical properties of uoropoly-mers it negatively impacts the surface wettability of the lms due to a decrease in the uorine content. A bilayer strategy reported here for the rst time consists of a relatively thick, mechanically-robust, and highly-cross-linked network which is covered with an ultrathin uorine-rich layer producing coatings with both enhanced mechanical properties and low surface energy which is essential for icephobic applications.…”

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confidence: 99%

Linker-free grafting of fluorinated polymeric cross-linked network bilayers for durable reduction of ice adhesion

2015

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Thin films of bilayer poly(divinyl benzene) p(DVB)/poly(perfluorodecylacrylate) (p-PFDA) are synthesized via iCVD on steel and silicon substrates. Nanomechanical measurements reveal that the elastic modulus and hardness of the films are enhanced through the bilayer structure and that the adhesion of the films to the substrate is improved via in situ grafting mechanism. The strength of ice adhesion to the treated surfaces is reduced more than six-fold when the substrates are coated with these bilayer polymer networks. 9 Icing can decrease efficiency in power production, result in mechanical and/or electrical failure, impact monitoring and control, and generate safety hazards.2,3,5,7 Active deicing methods that are employed to melt and break previously formed ice layers necessitate increased design complexity, may have detrimental environmental consequences, and require substantial power input for operation.10,11 Passive methods have recently been employed to protect exposed surfaces using icephobic coatings with characteristics designed to retard the formation of ice and facilitate the removal of ice deposits.3,9,12-22 Such coatings have been developed using solgel systems containing uorinated compounds and low surface energy rubbers, 20 lubricant-impregnated textured surfaces, 4 via hydrothermal reaction method, 23 low-pressure plasma polymerization, 24 and phase-separation methods. 7 However, a need remains for deposition methods that produce durable and mechanically-robust coatings over the large areas with enhanced adhesion to textured/rough surfaces that are commonly encountered in real world applications.In the present work, we have designed and synthesized for the rst time a mechanically-robust bilayer consisting of a thick and dense polymer base layer that is highly cross-linked and then capped with a covalently-attached thin icephobic uorine-rich top layer. We believe that the presence of a highly cross-linked polymer layer underneath a very thin u-oropolymer cap acts as a steric barrier resisting local surface reorganization, forcing the uorinated groups to remain on the surface even under wet conditions (Fig. S1, ESI †). In addition, the mechanical properties (for example the elastic modulus and hardness) of these customized bilayer polymer networks can be signicantly enhanced. Conceptual insightsIce formation and accumulation on surfaces can result in severe problems for solar photovoltaics, offshore oil platforms, wind turbines, and aircra. Practical adoption of icephobic surfaces requires mechanical robustness and stability under the harsh real-world environments. Here we design an icephobic surface using a bilayer strategy, optimizing the base layer for mechanical properties, while the top layer provides the desired high receding water contact angle (WCA). Both layers are formed sequentially by initiated chemical vapor deposition (iCVD) in the same reaction chamber. The iCVD polymerization of divinyl benzene (DVB) yields a cross-linked hydrocarbon base layer which is capped with an ultrathi...

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confidence: 99%

Linker-free grafting of fluorinated polymeric cross-linked network bilayers for durable reduction of ice adhesion

2015

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“…[11,13] The reactor was covered with a quartz top (2.5 cm thick) that allows real-time thickness monitoring by reflecting a 633 nm He-Ne laser source (JDS Uniphase) off the substrate/polymer and recording the interference signal intensity as a function of time. The reactor was pumped down by a mechanical Fomblin pump (Leybold, Trivac) and the pressure was monitored with a MKS capacitive gauge.…”

Section: Methodsmentioning

confidence: 99%

“…iCVD is a deposition technique that enables grafting of polymers to substrates and therefore promotes their adhesion to substrates to be durable against abrasion and erosion. [10][11][12] Unlike traditional polymer deposition techniques such as spin-coating, dipping, and ink-jet printing, iCVD provides ways to deposit graded polymers, copolymers which do not have common solvents, and multilayered polymers which are covalently bonded at their interface. [13,14] The conformal nature of the iCVD technique also enables the integration of polymer thin films onto engineering surfaces that have roughened features or nanostructured topography.…”

Section: Introductionmentioning

confidence: 99%

Designing Durable Vapor‐Deposited Surfaces for Reduced Hydrate Adhesion

Sojoudi

Walsh

Gleason

et al. 2015

Adv Materials Inter

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The formation and accumulation of clathrate hydrates inside oil and gas pipelines causes severe problems in deep-sea oil/gas operations. In the present work, durable and mechanically-robust bilayer poly-divinyl benzene (pDVB)/poly(perfluorodecylacrylate) (pPFDA) coatings are developed using initiated chemical vapor deposition (iCVD) to reduce the adhesion strength of hydrates to underlying substrates. Tetrahydrofuran (THF) dissolved in water with a wt. % concentration of 0-70 is used to study the formation of hydrates and their adhesion strength. Goniometric measurements of water droplets on the coated substrates exhibit advancing contact angles of 157.8º ± 2.3º and receding contact angles of 131º ± 8º, whereas 70 wt. % THF in water droplets present advancing angle of 85.1º ± 6.1º and receding angle of 48.5º ± 4.9º. The strength of hydrate adhesion experiences a ten-fold reduction when substrates are coated with these iCVD polymers: from 1050±250 kPa on bare substrates to 128±100 kPa on coated ones. The impact of subcooling temperature and time on the adhesion 2 strength of hydrate on substrates is also studied. The results of this work suggest that the THF-water mixture repellency of a given substrate can be utilized to assess its hydrate-phobic behavior; hence, it opens a pathway for studying hydrate-phobicity.

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“…Thus, the interaction between the polymer and its surroundings -either the substrate or the external environment -perpendicular to the surface modifying the wettability and roughness of the fi lm. A second study [ 26 ] revealed that grafting of PFDA polymer chains enhances the crystalline order of the coating, resulting in fi ber-like structures. The grafted fi lms exhibit superhydrophobic and oleophobic properties.…”

Section: Tailored Surfaces and Interfacesmentioning

confidence: 99%

Section: Tailored Surfaces and Interfacesmentioning

confidence: 99%

Chemical Vapor Deposition for Solvent‐Free Polymerization at Surfaces

Yagüe

Coclite

Petruczok

et al. 2012

Macro Chemistry & Physics

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Chemical vapor deposition (CVD) methods are a powerful technology for engineering surfaces. When CVD is combined with the richness of organic chemistry, the resulting polymeric coatings, deposited without solvents, represent an enabling technology in many different fi elds of application. This article focuses on initiated chemical vapor deposition (iCVD), a new technique that utilizes benign reaction conditions to yield conformal and functional polymer thin fi lms. The latest achievements in coating surfaces and 3D substrates with functional materials, and the use of the technique for biotechnology and selective permeation applications are reviewed, and future directions for iCVD technology are discussed.

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Grafted Crystalline Poly‐Perfluoroacrylate Structures for Superhydrophobic and Oleophobic Functional Coatings

Cited by 77 publications

References 25 publications

Linker-free grafting of fluorinated polymeric cross-linked network bilayers for durable reduction of ice adhesion

Linker-free grafting of fluorinated polymeric cross-linked network bilayers for durable reduction of ice adhesion

Designing Durable Vapor‐Deposited Surfaces for Reduced Hydrate Adhesion

Chemical Vapor Deposition for Solvent‐Free Polymerization at Surfaces

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