Waterborne Liquid-like Coatings with High Transparency, Superior Scratch Resistance, and Antismudge Properties.

The aqueous formulation of antismudge coatings is a crucial step for environmental protection and pollution reduction. However, the inferior mechanical durability of waterborne antismudge coatings poses challenges for their practical application. Herein, we developed a fully waterborne antismudge coating with excellent scratch resistance by preparing hyperbranched amine-rich polysiloxane (HySPx) for antismudge ability and epoxy-rich zirconium-based aqueous solution (ZAS) for mechanical performance. The former is obtained by combining SPx, polydimethylsiloxane modified by 3-isocyanatopropyltriethoxysilane (IPTS), with 3-aminopropyltriethoxysilane (KH550), and the latter is synthesized using zirconium propoxide solution (TPOZ) with 3-glycidyloxypropyltrimethoxysilane (KH560). This report investigates the effects of the chain length and content of SPx on the performance of the coating. The results indicate that the coating exhibits optimal comprehensive performance when the molecular weight of polydimethylsiloxane is 4.5 kDa, and the mass fraction of SPx in HySPx is 1.5%. The coating possesses high transparency similar to glass, good adhesion (≈3 MPa) to various substrates, high hardness (8H), flexibility (2.5 mm bending radius), and exceptional antismudge property. More importantly, the coating can still maintain excellent antismudge property even after enduring 400 cycles of abrasion with steel wool. Furthermore, the rapid enrichment of polydimethylsiloxane on the coating surface endows the coating with excellent lubrication ability, allowing most common liquid stains to slide off the coating surface. Moreover, the rewritability of the coating remains stable even after writing traces that have persisted on its surface for several weeks. This coating is anticipated to be utilized for protecting foldable electronic screens, vehicles, and other fields.

Solvent-Free and UV-Cured Epoxy Silicone Coating with Excellent Wear Resistance and Antismudge Properties.

Transparent, hard, and flexible multifunctional coatings have a wide range of applications; however, most of them need organic solvents. Here, we present a solvent-free and UV-cured coating made from fluorinated epoxy MTQ silicone resin combined with branched triepoxy siloxane as the reactive diluent. After UV-initiated ring-opening polymerization in the presence of a triarylsulfonium hexafluoroantimonate catalyst, the resultant cured coating exhibits high transparency (∼92%, 550 nm), pencil hardness (7H), and flexibility (1 mm bending diameter) due to the formed organic-inorganic nanostructures in a highly cross-linked network. The triepoxy siloxane significantly reduces the viscosity before curing and increases cross-link density of the coating. The coating without any volatile content shows a smooth surface with low roughness (Rq = 0.46 nm) and delivers an anti-smudge ability owing to perfluorinated chains inherited from the MTQ resin. Furthermore, even after 3000 abrasion cycles, the coating still has a water contact angle greater than 90°, displaying excellent wear resistance. Our work provides a promising way to access high-performance multifunctional coatings in a more sustainable manner.

Innovative Solid Slippery Coating: Uniting Mechanical Durability, Optical Transparency, Anti-Icing, and Anti-Graffiti Traits.

Slippery coatings, such as the slippery liquid-infused porous surface (SLIPS), have gained significant attention for their potential applications in anti-icing and anti-fouling. However, they lack durability when subjected to mechanical impact. In this study, we have developed a robust slippery coating by blending polyurethane acrylate (PUA) with methyltriethoxysilane (MTES) and perfluoropolyether (PFPE) in the solvent of butyl acetate. The resulting mixture is homogeneous and allows for uniform coating on various substrates using a drop coating process followed by drying at 160 °C for 3 h. The cured coating exhibits excellent water repellency (contact angle of ~108° and sliding angle of ~8°), high transparency (average visible transmittance of ~90%), exceptional adherence to the substrate (5B rating according to ASTMD 3359), and remarkable hardness (4H on the pencil hardness scale). Moreover, the coating is quite flexible and can be folded without affecting its wettability. The robustness of the coating is evident in its ability to maintain a sliding angle below 25° even when subjected to abrasion, water jetting, high temperature, and UV irradiation. Due to its excellent nonwetting properties, the coating can be employed in anti-icing, anti-graffiti, and anti-sticking applications. It effectively reduces ice adhesion on aluminum substrates from approximately 217 kPa to 12 kPa. Even after 20 cycles of icing and de-icing, there is only a slight increase in ice adhesion, stabilizing at 40 kPa. The coating can resist graffiti for up to 400 cycles of writing with an oily marker pen and erasing with a tissue. Additionally, the coating allows for easy removal of 3M tape thereon without leaving any residue.

Bio-Based Waterborne Polyurethane Coatings with High Transparency, Antismudge and Anticorrosive Properties.

Green and environment-friendly preparation are of the utmost relevance to the development of transparent antismudge coatings. To prepare a waterborne polyurethane (WPU) coating with antismudge property, it is challenging to balance the stability of dispersion and the antismudge property of coating. Herein, we prepare a transparent bio-based WPU coating grafted with a minor proportion of poly(dimethylsiloxane) (WPU-g-PDMS) using renewable castor oil, monocarbinol-terminated PDMS, hexamethylene diisocyanate trimer, and 2,2-bis(hydroxymethyl)propionic acid as raw materials. Effects of the dosage of monocarbinol-terminated PDMS, the curing temperature, and the curing time on the antismudge performance were studied. Results showed that rigorous stirring (3000 rpm) is necessary to obtain a stable WPU-g-PDMS dispersion with a storage time longer than 6 months. A high curing temperature (>160 °C) and a period of curing time (>1 h) are indispensable to obtain the excellent antismudge property because they would facilitate the grafted low-surface-tension PDMS chains to migrate from the interior to the coating surface. The facts that simulated contaminated liquids such as water, HCl solution, NaOH solution, artificial blood, and tissue fluid could slide off easily and cleanly, and marker ink lined on the coating surface could shrink, indicated that the WPU-g-PDMS coating has good antismudge properties, which could be self-compensated shortly after deterioration. Due to the high cross-linking degree caused by multifunctional polyol and isocyanate, the WPU-g-PDMS coating has high hardness and good anticorrosive performance. The antismudge functionalization and waterborne technology of bio-based polyurethane coatings proposed in this work could be a promising contribution to the green and sustainable development of functional coatings. This kind of WPU-g-PDMS coating is expected to protect and decorate electronic screens, vehicles, and buildings, especially endoscopes.

Anti-smudge and self-cleaning characteristics of waterborne polyurethane coating and its construction.

A novel anti-smudge coating, based on waterborne polyurethane (WPU), Polydimethylsiloxane (PDMS) and Hexamethoxymethylmelamine (HMMM) was constructed. Specifically, hydroxyl capped WPU emulsions grafted with PDMS (WPU-g-PDMSX) were prepared firstly, then the Hexamethoxymethylmelamine (HMMM) was used as the crosslinking agent to block the polar hydrophilic hydroxyl groups and the carboxyl groups in WPU-g-PDMSX and increase the cross-linking density of the coating. Oily markers, water, hexadecane, fingerprint liquid, and common liquids in life (milk, coffee, ink and cooking oil) were utilized to demonstrate the anti-graffiti and self-cleaning characteristics of coatings. Aside from having great transparency and exceptional resistance to liquid corrosion, the coating still retains its anti-smudge capabilities even when bent or impacted, and they also exhibit 5B adhesion and 5H pencil hardness. This work provides novel idea and strategy for the preparation of WPU anti-smudge coatings.

Facile Preparation of a Transparent and Rollable Omniphobic Coating with Exceptional Hardness and Wear Resistance.

The encapsulating film for the touchscreen of a foldable smartphone consists of a flexible polymer layer covered by a hard coating and an antismudge coating, and the two coating layers are currently deposited via separate steps. This paper reports the preparation of a bilayer bifunctional coating via the deposition of a single polymer mixture. The base material for the coating is a ladder-like polysilsesquioxane (LASQ) that is derived from the sol-gel chemistry of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Reacting a limiting amount of the liquid antismudge agent FP-COOH, which is a perfluorinated poly(propylene oxide) bearing a terminal carboxyl group, with LASQ yields m-LASQ-FP, a mixture of unreacted LASQ, and a graft copolymer LASQ-FP. m-LASQ-FP at a fluorine mass fraction of 6.0% is photocured to yield a coating with a surface energy of 12.3 ± 1.5 mJ/m2. At a thickness of 40 µm, the coating has at 500 nm a transmittance of >99% measured against its glass substrate, a remarkable nanoindentation hardness H value of 1.4 GPa, and a pencil hardness of > 9H. After being abraded for 300 strokes under a pressure of 26 kPa with steel wool, the coating exhibits no noticeable degradation in its ink contraction properties. At a thickness of 10 µm on a poly(ethylene terephthalate) film, the coating can undergo inward (on the inner surface of the bend) and outward bending to radii <1 and <2 mm, respectively, without cracking. Aside from being a superb candidate as a protective antismudge coating for foldable smartphones, this marvelous material should also have many other applications.

Fabrication of ultra-smooth hybrid thin coatings towards robust, highly transparent, liquid-repellent and antismudge coatings.

Liquid-repellent and anti-smudge coatings have a wide range of applications on the surface of materials. In this work, a novel liquid-repellent anti-smudge hybrid coating was in situ fabricated by using tetraethyl orthosilicate (TEOS) and dimethoxydimethylsilane (DMDEOS) under acid catalysis. The resulting coatings had a high transmittance of 3-4% higher than that of blank glass. The superior smoothness and high mobility of generated poly(dimethyl siloxane) (PDMS) chains on the surface resulted in low sliding angles of 4.5° (water) and 2.8° (n-hexadecane), and a high water sliding velocity of 15.6 cm s-1 at a tilting angle of 70°. In addition, the hybrid coatings could repel both ink and dust contaminations and hinder bacteria adhesion. What's more, the anti-smudge coatings demonstrated excellent durability and mechanical properties of 8H pencil hardness and 5A adhesion grade. Thus, a new perspective is provided for the preparation of anti-smudge coatings. The simple preparation method would bring a breakthrough in the development and application of anti-smudge materials.

Robust Hybrid Omniphobic Surface for Stain Resistance.

Inspired by natural living surfaces, researchers have developed many excellent anti-smudge coatings, but there remain some critical challenges such as complex or expensive fabrications, poor long-term stability, non-transparency, etc., which may limit their large-area application. In this work, we designed a robust and transparent omniphobic coating with a one-step dip coating method. The perfluoropolyether chains were grafted on a smooth glass surface, and the coating surface not only presented good liquid repellency and stain resistance but also owned excellent mechanical wear resistance. The stain resistance property and wettability have barely changed after hundreds of thousands of friction cycles in air or even in an organic solvent surrounding. The robust hybrid coating possesses simple preparation, an excellent property, and durability, which may bring a widespread interest in the engineering application field.

Robust Hyperbranched Polyester-Based Anti-Smudge Coatings for Self-Cleaning, Anti-Graffiti, and Chemical Shielding.

In this work, a novel anti-smudge coating system was developed by using hydroxyl-terminated hyperbranched polyester as a coating precursor, mono-hydroxyl-terminated poly(dimethylsiloxane) (PDMS) as an anti-smudge agent, and hexamethylene diisocyanate trimer as a curing agent. The resultant coatings with 0.5 wt % PDMS content incorporated are highly transparent and liquid repellent. They exhibit striking repellency against various liquids and display remarkable self-cleaning performance. Water, hexadecane, salt solution, strong alkali solution, strong acid solution, pump oil, and crude oil could slide off the coated surface without leaving any traces, and the dirt on the coated surface could be readily removed by water or oil. Besides, these coatings show potential application for anti-fingerprint and anti-graffiti due to the exceptional repellency of coated surface against artificial fingerprint liquid, oil-based ink, paint, and water-based smudge. Furthermore, they also possess superb chemical shielding ability and thus endow substrates with remarkable protection against exposure to harsh chemical conditions. Moreover, these coatings are mechanically robust against extensive abrasion, impact, and bending without compromising anti-smudge properties, and they also exhibit excellent adhesion to various substrates. Therefore, these newly developed coatings have tremendous potential for widespread applications.

UV-Curable Antismudge Coatings.

Current antismudge coatings that bear nano-pools of a grafted liquid ingredient for dewetting enablement (NP-GLIDE) are cured at high temperatures, which are undesirable for application on heat-sensitive substrates. Reported herein is the development of a NP-GLIDE coating that can be photocured at room temperature. Of the various formulations that have been tested, robust coatings were obtained from one recipe consisting of a photoinitiator, a trifunctional monomer that bears three double bonds, and a graft copolymer. The last bears pendent double bonds and a poly(dimethylsiloxane) (PDMS) side chain as the antismudge agent. Coatings were prepared by casting films from a solution containing these three components and then photolyzing the resultant films. A systematic study revealed that the liquid sliding property developed on the coating at a lower cross-linking density than that required for ink to contract. Further, retaining the ability to contract ink traces after many writing and erasing cycles was the most demanding of the three antismudge tests. For our optimized formulation, only 5 min of irradiation was required to yield a transparent coating with superior antismudge properties. Moreover, irradiating selected regions and then removing, with a solvent, reagents in the nonirradiated regions can yield a surface with patterned wettability. These advantageous properties of the new photocurable coating facilitate its applications.

Silicone-Infused Antismudge Nanocoatings.

A polyurethane-based NP-GLIDE coating that bears on its surface and in its interior nano-pools of a grafted liquid ingredient for dewetting enablement is obtained from casting and curing a film comprising a triisocyanate, a polyol (P1), and a graft (g) copolymer of P1 and poly(dimethylsiloxane) (P1-g-PDMS). A silicone-infused NP-GLIDE (SINP-GLIDE) PU coating is obtained from cocasting the NP-GLIDE precursors with a free silicone oil (SO) or SO mixture (SOs). This paper reports the preparation of the novel SINP-GLIDE coatings and discusses the effect of changing the amount and type of the infused SO as well as the coating formation conditions on their optical clarity. Also reported are the contact and sliding angles of various test liquids on the NP-GLIDE and SINP-GLIDE coatings, and the data variation trends are rationalized using existing theories. Further, the stable water sliding performance of the SINP-GLIDE coatings under simulated raining and other conditions is demonstrated. The improved and stable water sliding performance of the SINP-GLIDE coatings facilitates their practical applications.

Mechanically durable superoleophobic aluminum surfaces with microstep and nanoreticula hierarchical structure for self-cleaning and anti-smudge properties.

Superoleophobic aluminum surfaces are of interest for self-cleaning, anti-smudge (fingerprint resistance), anti-fouling, and corrosion resistance applications. In the published literature on superoleophobic aluminum surfaces, mechanical durability, self-cleaning, and anti-smudge properties data are lacking. Microstep structure has often been used to prepare superhydrophobic aluminum surfaces which produce the microstructure. The nanoreticula structure has also been used, and is reported to be able to trap air-pockets, which are desirable for a high contact angle. In this work, the microstep and nanoreticula structures were produced on aluminum surfaces to form a hierarchical micro/nanostructure by a simple two-step chemical etching process. The hierarchical structure, when modified with fluorosilane, made the surface superoleophobic. The effect of nanostructure, microstructure, and hierarchical structure on wettability and durability were studied and compared. The superoleophobic aluminum surfaces were found to be wear resistant, self-cleaning, and have anti-smudge and corrosion resistance properties.

Fluorine-Free Anti-Smudge Polyurethane Coatings.

Conventionally, low-surface-tension fluorinated reagents are incorporated into anti-smudge (oil- and water-repellent) coatings for oil repellency. However, fluorinated compounds are expensive and an environmental concern because of their high stability and bioaccumulation. These factors limit their widespread application. We report herein the development of fluorine-free anti-smudge polyurethane coatings that are clear at thicknesses up to tens of micrometers and are able to sustain extensive surface damage. We demonstrate that these coatings can be applied readily onto a diverse range of substrates.

Mechanically durable, superomniphobic coatings prepared by layer-by-layer technique for self-cleaning and anti-smudge.

Superomniphobic surfaces are of interest for anti-fouling, self-cleaning, anti-smudge and low-drag applications. Many bioinspired surfaces developed previously are of limited use due to a lack of mechanical durability. From a previously developed technique, an adapted layer-by-layer approach involving charged species with electrostatic interactions between layers is combined with an uncharged fluorosilane layer to result in a durable, superomniphobic coating. This technique can provide the flexibility needed to improve adhesion to the substrate with the addition of a low surface tension coating at the air interface. In this work, polyelectrolyte binder, SiO2 nanoparticles, and fluorosilane layers are deposited, providing the combination of surface roughness and low surface tension to result in a superomniphobic coating with droplets of liquids with surface tensions from 72 to 21 mN m(-1) displaying contact angles exceeding 155° with low tilt angles. The durability of these coatings was examined through the use of micro- and macrowear experiments. These coatings currently display levels of transparency acceptable for automotive applications. Fabrication via this novel combination of techniques results in durable, superomniphobic coatings displaying improved performance compared to existing work where either the durability or the repellency is compromised.

Wear-resistant and antismudge superoleophobic coating on polyethylene terephthalate substrate using SiO2 nanoparticles.

It is of interest to create superoleophobic surfaces that exhibit high oil contact angle, low contact angle hysteresis, high wear resistance, antismudge properties, and optical transparency for industrial applications. In the superoleophobic surfaces developed to date, the mechanical durability data is lacking. By dip-coating polyethylene terephthalate substrate with hydrophobic SiO2 nanoparticles and methylphenyl silicone resin, followed by O2 plasma treatment and vapor deposition of 1H,1H,2H,2H-perfluorooctyltrichlorosilane, a durable superoleophobic surface was fabricated. The degree of superoleophobicity was found to be dependent on the particle-to-binder ratio. The coatings were found to exhibit wear resistance on microscale and macroscale, antismudge properties, and transparency.

Dual-layered-coated mechanically-durable superomniphobic surfaces with anti-smudge properties.

Bio-inspired surfaces that exhibit high contact angle and low contact angle hysteresis for various liquids and demonstrate mechanical durability and anti-smudge properties are of interest for various applications. The fabrication of such surfaces has often involved complex or expensive processes, required techniques that may not be suitable for various substrates and particles, may require surface post-treatment, or may lack durability. Dual layered coatings of roughness-induced superomniphobic surfaces that demonstrate good mechanical durability were fabricated on glass substrates using hydrophobic SiO2 nanoparticles and low surface energy fluorobinders using dip coating and spray coating techniques. The particle-to-binder ratio was optimized for contact angles of interest. The mechanical durability of these coatings was examined under mechanical rubbing action. The anti-smudge properties were examined by wiping an artificially contaminated coating using oil-impregnated microfiber cloth.