Integration of Self‐Lubrication and Near‐Infrared Photothermogenesis for Excellent Anti‐Icing/Deicing Performance

The economic and safety issues caused by ice accretion have become more and more serious. Except for traditional ways of anti‐icing, such as spraying agents, mechanical/thermal removal, etc., more economic approaches are urgently required. This work demonstrates the conceptual feasibility of using a self‐lubricated photothermal coating for both anti‐icing and deicing function. The coating is generally water repellent and infiltrated with hydrocarbon or perfluorocarbon oils as the lubricant to endow a liquid interface for preventing ice accumulation and minimizing the adhesion of ice on surfaces once it is formed. Fe₃O₄ nanoparticles are added to the film to afford high efficiency photothermal effect under near‐infrared irradiation for rapidly melting the accumulated ice. The conceptual strategy can be easily implemented as a facile method to fabricate analogous sprayed coatings. It represents a major advance to tackle the challenging icing issue that is normally seen as a disaster in everyday life.     

Anti‐liquid‐Interfering and Bacterially Antiadhesive Strategy for Highly Stretchable and Ultrasensitive Strain Sensors Based on Cassie‐Baxter Wetting State

As a large number of strain sensors are put into practical use, their stability should be considered, especially in harsh environments containing water or microorganisms, which could affect strain sensing. Herein, a novel strategy to overcome liquid interference is proposed. The strain sensor is constructed with a sandwich architecture through layer‐by‐layer (LBL) spray‐coating of a 3‐(aminopropyl)triethoxysilane (APTES) bonding layer and multi‐walled carbon nanotubes/graphene (MWCNT/G) conductive layers on an elastomeric polydimethysiloxane (PDMS) substrate, and is further decorated with silver (Ag) nanoparticles and the (heptadecafluoro‐1,1,2,2‐tetradecyl) trimethoxysilane (FAS, F in short) to obtain a F/Ag/MWCNG/G‐PDMS (FAMG) strain sensor. The superhydrophobicity and underwater oleophobicity of the outer cover layer causes this FAMG strain sensor surface to exhibit stable strain sensing resistant to liquid interference upon stretching in the Cassie?Baxter wetting state, and resistance to bacterial adhesion (Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli)). The sensor attains ultrasensitivity (with a maximum gauge factor of 1989 in the condition of liquid interference), broad strain range (0.1–170%), fast response time (150 ms), and stable response after 1000 stretching–releasing cycles. The ultrasensitivity is provided by propagation of cracks in MWCNT/G conductive layers and terminal fracture of the intermediate separating layers (APTES/MWCNT/G). The microbridge effect of MWCNTs and slippage of APTES/MWCNT/G provide a large strain range. The FAMG strain sensor is successfully used to monitor a series of human activities and an electronic bird under artificial rain and bacterial droplets, indicating the potential use of this sensor in complex environments.     

Controlled Release of LL‐37‐Derived Synthetic Antimicrobial and Anti‐Biofilm Peptides SAAP‐145 and SAAP‐276 Prevents Experimental Biomaterial‐Associated Staphylococcus aureus Infection

The present study aims to develop an implant coating releasing novel antimicrobial agents to prevent biomaterial‐associated infections. The LL‐37‐derived synthetic antimicrobial and anti‐biofilm peptides (SAAP)‐145 and SAAP‐276 exhibit potent bactericidal and anti‐biofilm activities against clinical and multidrug‐resistant Staphylococcus aureus strains by rapid membrane permeabilization, without inducing resistance. Injection of SAAP‐145, but not SAAP‐276, along subcutaneous implants in mice reduces S. aureus implant colonization by approximately 2 log, but does not reduce bacterial numbers in surrounding tissue. To improve their efficacy, SAAP‐145 and SAAP‐276 are incorporated in a polymer–lipid encapsulation matrix (PLEX) coating, providing a constant release of 0.6% daily up to 30 d after an initial burst release of >50%. In a murine model for biomaterial‐associated infection, SAAP‐145‐PLEX and SAAP‐276‐PLEX coatings significantly reduce the number of culture positive implants and show ≥3.5 and ≥1.5 log lower S. aureus implant and tissue colonization, respectively. Interestingly, these peptide coatings are also highly effective against multidrug‐resistant S. aureus, both reducing implant colonization by ≥2 log. SAAP‐276‐PLEX additionally reduces tissue colonization by 1 log. Together, the peptide‐releasing PLEX coatings hold promise for further development as an alternative to coatings releasing conventional antibiotics to prevent biomaterial‐associated infections.     

Photoresponsive Sponge‐Like Coating for On‐Demand Liquid Release

Many publications report on stimuli responsive coatings, but only a few on the controlled release of species in order to change the coating surface properties. A sponge‐like coating that is able to release and absorb a liquid upon exposure to light has been developed. The morphology of the porous coating is controlled by the smectic liquid crystal properties of the monomer mixture prior to its polymerization, and homeotropic order is found to give the largest contraction. The fast release of the liquid can be induced by a macroscopic contraction of the coating caused by a trans to cis conversion of a copolymerized azobenzene moiety. The liquid secretion can be localized by local light exposure or by creating a surface relief. The uptake of liquid proceeds by stimulating the back reaction of the azo compound by exposure at higher wavelength or by thermal relaxation. The surface forces of the sponge‐like coating in contact with an opposing surface can be controlled by light‐induced capillary bridging revealing that the controlled release of liquid gives access to tunable adhesion.     

Enhanced Omnidirectional Photovoltaic Performance of Solar Cells Using Multiple‐Discrete‐Layer Tailored‐ and Low‐Refractive Index Anti‐Reflection Coatings

An optimized four‐layer tailored‐ and low‐refractive index anti‐reflection (AR) coating on an inverted metamorphic (IMM) triple‐junction solar cell device is demonstrated. Due to an excellent refractive index matching with the ambient air by using tailored‐ and low‐refractive index nanoporous SiO₂ layers and owing to a multiple‐discrete‐layer design of the AR coating optimized by a genetic algorithm, such a four‐layer AR coating shows excellent broadband and omnidirectional AR characteristics and significantly enhances the omnidirectional photovoltaic performance of IMM solar cell devices. Comparing the photovoltaic performance of an IMM solar cell device with the four‐layer AR coating and an IMM solar cell with the conventional SiO₂/TiO₂ double layer AR coating, the four‐layer AR coating achieves an angle‐of‐incidence (AOI) averaged short‐circuit current density, J_SC, enhancement of 34.4%, whereas the conventional double layer AR coating only achieves an AOI‐averaged J_SC enhancement of 25.3%. The measured reflectance reduction and omnidirectional photovoltaic performance enhancement of the four‐layer AR coating are to our knowledge, the largest ever reported in the literature of solar cell devices.     

Liquid‐Infused Smooth Coating with Transparency,Super‐Durability,and Extraordinary Hydrophobicity

Liquid‐infused coatings are because of their fluidity of considerable technological importance for hydrophobic materials with multifunctional properties, such as self‐healing, transmittance, and durability. However, conventional coatings absorb viscous liquid into their sponge‐like structured surface, causing uncontrollable liquid layer formation or liquid transport. In addition, a hydrophobic‐liquid‐retained surface can cause instability and lead to limitation of the hydrophobicity, optical properties, and flexibility due to liquid layer evaporation. Here, we report a strategy for controllable liquid‐layer formation on smooth surfaces (R _rms < 1 nm) by π ‐electron interactions. Using this technology, superoleophilic wetting of decyltrimethoxysilane results in the design of a surface with π ‐interaction liquid adsorption, smoothness, and hydrophobicity (SPLASH), that shows extraordinary hydrophobicity (CAH = 0.75°), and stable repellence for various water‐based solutions including micrometer‐sized mist. The smoothness of the solid under a liquid layer enabled the SPLASH to exhibit stable hydrophobicity, transparency (>90%), structure damage durability and flexibility, regardless of the liquid layer thickness by bending or evaporation. Furthermore, the patterned π ‐electrons' localization on the smooth coating enables controlled liquid‐layer formation and liquid transport. This strategy may provide new insights into designing functional liquid surfaces and our designed surface with multifunctional properties could be developed for various applications.     

A Shape‐Adaptive,Antibacterial‐Coating of Immobilized Quaternary‐Ammonium Compounds Tethered on Hyperbranched Polyurea and its Mechanism of Action

Quaternary‐ammonium‐compounds are potent cationic antimicrobials used in everyday consumer products. Surface‐immobilized, quaternary‐ammonium‐compounds create an antimicrobial contact‐killing coating. We describe the preparation of a shape‐adaptive, contact‐killing coating by tethering quaternary‐ammonium‐compounds onto hyperbranched polyurea coatings, able to kill adhering bacteria by partially enveloping them. Even after extensive washing, coatings caused high contact‐killing of Staphylococcus epidermidis, both in culture‐based assays and through confocal‐laser‐scanning‐microscopic examination of the membrane‐damage of adhering bacteria. In culture‐based assays, at a challenge of 1600 CFU/cm², contact‐killing was >99.99%. The working‐mechanism of dissolved quaternary‐ammonium‐compounds is based on their interdigitation in bacterial membranes, but it is difficult to envisage how immobilized quaternary‐ammonium‐molecules can exert such a mechanism of action. Staphylococcal adhesion forces to hyperbranched quaternary‐ammonium coatings were extremely high, indicating that quaternary‐ammonium‐molecules on hyperbranched polyurea partially envelope adhering bacteria upon contact. These lethally strong adhesion forces upon adhering bacteria then cause removal of membrane lipids and eventually lead to bacterial death.     

Polycationic Synergistic Antibacterial Agents with Multiple Functional Components for Efficient Anti‐Infective Therapy

Multifunctional antibacterial photodynamic therapy is a promising method to combat regular and multidrug‐resistant bacteria. In this work, eosin Y (EY)‐based antibacterial polycations (EY‐QEGED? R, R = ? CH₃ or ? C₆H₁₃) with versatile types of functional components including quaternary ammonium, photosensitizer, primary amine, and hydroxyl species are readily synthesized based on simple ring‐opening reactions. In the presence of light irradiation, such antibacterial polymers exhibit high antibacterial efficiency against both Escherichia coli and Staphylococcus aureus. In particular, EY‐QEGED? R elicits a remarkable synergistic antibacterial activity owing to the combined photodynamic and quaternary ammonium antibacterial effects. Due to its rich primary amine groups, EY‐QEGED? R also can be readily coated on different substrates, such as glass slides and nonwoven fabrics via an adhesive layer of polydopamine. The resultant surface coating of EY‐QEGED? CH₃ (s‐EY‐QEGED? CH₃) produces excellent in vitro antibacterial efficacy. The plentiful hydroxyl groups impart s‐EY‐QEGED? CH₃ with potential antifouling capability against dead bacteria. The antibacterial polymer coatings also demonstrate low cytotoxicity and good hemocompatibility. More importantly, s‐EY‐QEGED? CH₃ significantly enhances in vivo therapeutic effects on an infected rat model. The present work provides an efficient strategy for the rational design of high‐performance antibacterial materials to fight biomedical device‐associated infections.     

Omniphobic “RF Paper” Produced by Silanization of Paper with Fluoroalkyltrichlorosilanes

The fabrication and properties of “fluoroalkylated paper” (“R^F paper”) by vapor‐phase silanization of paper with fluoroalkyl trichlorosilanes is reported. R^F paper is both hydrophobic and oleophobic: it repels water (θ_app^H2^O>140°), organic liquids with surface tensions as low as 28 mN m^‐1, aqueous solutions containing ionic and non‐ionic surfactants, and complex liquids such as blood (which contains salts, surfactants, and biological material such as cells, proteins, and lipids). The propensity of the paper to resist wetting by liquids with a wide range of surface tensions correlates with the length and degree of fluorination of the organosilane (with a few exceptions in the case of methyl trichlorosilane‐treated paper), and with the roughness of the paper. R^F paper maintains the high permeability to gases and mechanical flexibility of the untreated paper, and can be folded into functional shapes (e.g., microtiter plates and liquid‐filled gas sensors). When impregnated with a perfluorinated oil, R^F paper forms a “slippery” surface (paper slippery liquid‐infused porous surface, or “paper SLIPS“) capable of repelling liquids with surface tensions as low as 15 mN m^‐1. The foldability of the paper SLIPS allows the fabrication of channels and flow switches to guide the transport of liquid droplets.     

Polymer‐Stabilized Chromonic Liquid‐Crystalline Polarizer

Robust coatable polarizer is fabricated by the self‐assembly of lyotropic chromonic liquid crystals and subsequent photo‐polymerizing processes. Their molecular packing structures and optical behaviors are investigated by the combined techniques of microscopy, scattering and spectroscopy. To stabilize the oriented Sunset Yellow FCF (H‐SY) films and to minimize the possible defects generated during and after the coating, acrylic acid (AA) is added to the H‐SY/H₂O solution and photo‐polymerized. Utilizing cross‐polarized optical microscopy, phase behaviors of the H‐SY/H₂O/AA solution are monitored by varying the compositions and temperatures of the solution. Based on the experimental results of two‐dimensional wide angle X‐ray diffraction and selected area electron diffraction, the H‐SY crystalline unit cell is determined to be a monoclinic structure with the dimensions of a = 1.70 nm, b = 1.78 nm, c = 0.68 nm, α = β = 90.0° and γ = 84.5°. The molecular arrangements in the oriented H‐SY films were further confirmed by polarized Fourier‐transform infrared spectroscopy. The polymer‐stabilized H‐SY films show good mechanical and chemical stabilities with a high polarizability. Additionally, patterned polarizers are fabricated by applying a photo‐mask during the photo‐polymerization of AA, which may open new doors for practical applications in electro‐optic devices.     

High‐Performance Solution‐Processable Poly(p‐phenylene vinylene)s for Air‐Stable Organic Field‐Effect Transistors

The influence of the substitution pattern (unsymmetrical or symmetrical), the nature of the side chain (linear or branched), and the processing of several solution processable alkoxy‐substituted poly(p‐phenylene vinylene)s (PPVs) on the charge‐carrier mobility in organic field‐effect transistors (OFETs) is investigated. We have found the highest mobilities in a class of symmetrically substituted PPVs with linear alkyl chains (e.g., R¹, R² = n‐C₁₁H₂₃, R³ = n‐C₁₈H₃₇). We have shown that the mobility of these PPVs can be improved significantly up to values of 10^–2 cm² V^–1 s^–1 by annealing at 110 °C. In addition, these devices display an excellent stability in air and dark conditions. No change in the electrical performance is observed, even after storage for thirty days in humid air.     

Filefish‐Inspired Surface Design for Anisotropic Underwater Oleophobicity

Surfaces with anisotropic wettability, widely found in nature, have inspired the development of one‐dimensional water control on surfaces relying on the well‐arranged surface features. Controlling the wetting behavior of organic liquids, especially the motion of oil fluid on surfaces, is of great importance for a broad range of applications including oil transportation, oil‐repellent coatings, and water/oil separation. However, anisotropic oil‐wetting surfaces remain unexplored. Here, the unique skin of a filefish Navodon septentrionalis shows anisotropic oleophobicity under water. On the rough skin of N. septentrionalis, oil droplets tend to roll off in a head‐to‐tail direction, but pin in the opposite direction. This pronounced wetting anisotropy results from the oriented hook‐like spines arrayed on the fish skin. It inspires further exploration of the artificial anisotropic underwater oleophobic surfaces: By mimicking the oriented hook‐like microstructure on a polydimethylsiloxane layer via soft lithography and subsequent oxygen‐plasma treatment to make the PDMS hydrophilic, artificial fish skin is fabricated which has similar anisotropic underwater oleophobicity. Drawn from the processing of artificial fish skin, a simple principle is proposed to achieve anisotropic underwater oleophobicity by adjusting the hydrophilicity of surface composition and the anisotropic microtextures. This principle can guide the simple mass manufacturing of various inexpensive high surface‐energy materials, and the principle is demonstrated on commercial cloth corduroy. This study will profit broad applications involving low‐energy, low‐expense oil transportation, underwater oil collection, and oil‐repellant coatings on ship hulls and oil pipelines.     

Lubricant‐Infused Nanoparticulate Coatings Assembled by Layer‐by‐Layer Deposition

Omniphobic coatings are designed to repel a wide range of liquids without leaving stains on the surface. A practical coating should exhibit stable repellency, show no interference with color or transparency of the underlying substrate and, ideally, be deposited in a simple process on arbitrarily shaped surfaces. We use layer‐by‐layer (LbL) deposition of negatively charged silica nanoparticles and positively charged polyelectrolytes to create nanoscale surface structures that are further surface‐functionalized with fluorinated silanes and infiltrated with fluorinated oil, forming a smooth, highly repellent coating on surfaces of different materials and shapes. We show that four or more LbL cycles introduce sufficient surface roughness to effectively immobilize the lubricant into the nanoporous coating and provide a stable liquid interface that repels water, low‐surface‐tension liquids and complex fluids. The absence of hierarchical structures and the small size of the silica nanoparticles enables complete transparency of the coating, with light transmittance exceeding that of normal glass. The coating is mechanically robust, maintains its repellency after exposure to continuous flow for several days and prevents adsorption of streptavidin as a model protein. The LbL process is conceptually simple, of low cost, environmentally benign, scalable, automatable and therefore may present an efficient synthetic route to non‐fouling materials.     

Spin‐Coated Highly Efficient Phosphorescent Organic Light‐Emitting Diodes Based on Bipolar Triphenylamine‐Benzimidazole Derivatives

A new series of star‐shaped bipolar host molecules, tris(4′‐(1‐phenyl‐1H‐benzimidazol‐2‐yl)biphen‐yl‐4‐yl) amine (TIBN), tris(2′‐methyl‐4′‐(1‐phenyl‐1H‐benzimida zol‐2‐yl)biphenyl‐4‐yl)amine (Me‐TIBN), and tris(2,2′‐dimethyl‐4′‐(1‐phenyl‐1H‐benzimidazol‐2‐yl)biphenyl‐4‐yl)amine (DM‐TIBN), that contain hole‐transporting triphenylamine and electron‐transporting benzimidazole moieties are designed based on calculations using density functional theory and successfully prepared. The theoretical calculation of energy levels of TIBN derivatives affords helpful ideas to design molecules with a favorable localization of highest occupied/lowest unoccupied molecular orbital (HOMO/LUMO) levels and a predefined enhancement of the triplet energy gap. The TIBN derivatives are employed as hosts to fabricate phosphorescent organic light‐emitting diodes (OLEDs) by the two methods of spin‐coating and vacuum deposition. Notably, the spin‐coated Me‐TIBN and DM‐TIBN devices exhibit a much better performance than the vacuum‐deposited ones, in which the spin‐coated DM‐TIBN device (47 500 cd m^?2, 27.3 cd A^?1, 7.3 lm W^?1) is outstanding with respect to other seminal work for solution‐processed OLEDs. More importantly, the new concept of localizing HOMO and LUMO levels for bipolar molecules is illustrated, and a facile strategy to tailor the energy levels by breaking the conjugation of hole‐ and electron‐transporting moieties is demonstrated.     

Anti‐Oxygen Leaking LiCoO2

LiCoO₂ is a prime example of widely used cathodes that suffer from the structural/thermal instability issues that lead to the release of their lattice oxygen under nonequilibrium conditions and safety concerns in Li‐ion batteries. Here, it is shown that an atomically thin layer of reduced graphene oxide can suppress oxygen release from Li_xCoO₂ particles and improve their structural stability. Electrochemical cycling, differential electrochemical mass spectroscopy, differential scanning calorimetry, and in situ heating transmission electron microscopy are performed to characterize the effectiveness of the graphene‐coating on the abusive tolerance of Li_xCoO₂. Electrochemical cycling mass spectroscopy results suggest that oxygen release is hindered at high cutoff voltage cycling when the cathode is coated with reduced graphene oxide. Thermal analysis, in situ heating transmission electron microscopy, and electron energy loss spectroscopy results show that the reduction of Co species from the graphene‐coated samples is delayed when compared with bare cathodes. Finally, density functional theory and ab initio molecular dynamics calculations show that the rGO layers could suppress O₂ formation more effectively due to the strong C? O_cathode bond formation at the interface of rGO/LCO where low coordination oxygens exist. This investigation uncovers a reliable approach for hindering the oxygen release reaction and improving the thermal stability of battery cathodes.     

Refining Energy Levels in ReS2 Nanosheets by Low‐Valent Transition‐Metal Doping for Dual‐Boosted Electrochemical Ammonia/Hydrogen Production

Electrocatalytic nitrogen reduction reaction (NRR) and hydrogen evolution reaction (HER) are intriguing approaches to nitrogen fixation and hydrogen production under ambient conditions, given the need to discover efficient and stable catalysts to light up the “green chemistry” future. However, bottlenecks are often found during N₂/H₂O activation, the very first step of NRR/HER, due to energetic electron injection from the surface of electrocatalysts. It is reported that the bottlenecks for both NRR and HER can be tackled by engineering the energy level via low‐valent transition‐metal doping, simultaneously, where rhenium disulfide (ReS₂) is employed as a model platform to prove the concept. The doped low‐valent transition‐metal domains (e.g., Fe, Co, Ni, Cu, Zn) in ReS₂ provide more active sites for N₂/H₂O chemisorption and electron transfer, not only weakening the N?N/O? H bonds for easier dissociation through proton coupling, but also elevating d‐band center toward the Fermi level with more electron energy for N₂/H₂O reduction. As a result, it is found that iron‐doped ReS₂ nanosheets wrapped nitrogen‐doped carbon nanofiber (Fe‐ReS₂@N‐CNF) catalyst exhibits superior electrochemical activity with eightfold higher ammonia production yield of 80.4 µg h^?1 mg^?1_cat., and lower onset overpotential of 146 mV and Tafel slope of 63 mV dec^?1, when comparing with the pristine ReS₂.     

Co‐Percolating Graphene‐Wrapped Silver Nanowire Network for High Performance,Highly Stable,Transparent Conducting Electrodes

Transparent conducting electrodes (TCEs) require high transparency and low sheet resistance for applications in photovoltaics, photodetectors, flat panel displays, touch screen devices and imagers. Indium tin oxide (ITO), or other transparent conductive oxides, have typically been used, and provide a baseline sheet resistance (R_S) vs. transparency (T) relationship. However, ITO is relatively expensive (due to limited abundance of Indium), brittle, unstable, and inflexible; moreover, ITO transparency drops rapidly for wavelengths above 1000 nm. Motivated by a need for transparent conductors with comparable (or better) R_S at a given T, as well as flexible structures, several alternative material systems have been investigated. Single‐layer graphene (SLG) or few‐layer graphene provide sufficiently high transparency (≈97% per layer) to be a potential replacement for ITO. However, large‐area synthesis approaches, including chemical vapor deposition (CVD), typically yield films with relatively high sheet resistance due to small grain sizes and high‐resistance grain boundaries (HGBs). In this paper, we report a hybrid structure employing a CVD SLG film and a network of silver nanowires (AgNWs): R_S as low as 22 Ω/□ (stabilized to 13 Ω/□ after 4 months) have been observed at high transparency (88% at λ = 550 nm) in hybrid structures employing relatively low‐cost commercial graphene with a starting R_S of 770 Ω/□. This sheet resistance is superior to typical reported values for ITO, comparable to the best reported TCEs employing graphene and/or random nanowire networks, and the film properties exhibit impressive stability under mechanical pressure, mechanical bending and over time. The design is inspired by the theory of a co‐percolating network where conduction bottlenecks of a 2D film (e.g., SLG, MoS₂) are circumvented by a 1D network (e.g., AgNWs, CNTs) and vice versa. The development of these high‐performance hybrid structures provides a route towards robust, scalable and low‐cost approaches for realizing high‐performance TCE.     

Paper‐Based Surfaces with Extreme Wettabilities for Novel,Open‐Channel Microfluidic Devices

In this work, a facile methodology is discussed, involving fluoro‐silanization followed by oxygen plasma etching, for the fabrication of surfaces with extreme wettabilities, i.e., surfaces that display all four possible combinations of wettabilities with water and different oils: hydrophobic–oleophilic, hydrophilic–oleophobic, omniphobic, and omniphilic. Open‐channel, paper‐based microfluidic devices fabricated using these surfaces with extreme wettabilities allow for the localization, manipulation, and transport of virtually all high‐ and low‐surface tension liquids. This in turn expands the utility of paper‐based microfluidic devices to a range of applications never before considered. These include, as demonstrated here, continuous oil–water separation, liquid–liquid extraction, open‐channel microfluidic emulsification, microparticle fabrication, and precise measurement of mixtures' composition. Finally, the biocompatibility of the developed microfluidic devices and their utility for cell patterning are demonstrated.     

Application of Inhibitor‐Loaded Halloysite Nanotubes in Active Anti‐Corrosive Coatings

Halloysite particles are aluminum‐silicate hollow cylinders with a length of 0.5–1 µm, an outer diameter of ca. 50 nm and a lumen of 15 nm. These nanotubes are used for loading and sustained release of corrosion inhibitors. The inhibitor is kept inside the particles infinitely long under dry conditions. Here, halloysite nanotubes filled with anticorrosive agents are embedded into a SiO_x–ZrO_x hybrid film. An aluminum plate is dip‐coated and immersed into 0.1 M sodium chloride aqueous solution for corrosion tests. A defect in the sol–gel coating induces pitting corrosion on the metal accompanied by a strong anodic activity. The inhibitor is released within one hour from halloysite nanotubes at corrosion spots and suppresses the corrosion process. The anodic activity is successfully restrained and the protection remains for a long time period of immersion in NaCl water solution. The self‐healing effect of the sol–gel coating doped with inhibitor‐loaded halloysite nanotubes is demonstrated in situ via scanning vibrating electrode technique measurements.     

Double Stimuli‐Responsive Isoporous Membranes via Post‐Modification of pH‐Sensitive Self‐Assembled Diblock Copolymer Membranes

Double stimuli‐responsive membranes are prepared by modification of pH‐sensitive integral asymmetric polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) diblock copolymer membranes with temperature‐responsive poly(N‐isopropylacrylamide) (pNIPAM) by a surface linking reaction. PS‐b‐P4VP membranes are first functionalized with a mild mussel‐inspired polydopamine coating and then reacted via Michael addition with an amine‐terminated pNIPAM‐NH₂ under slightly basic conditions. The membranes are thoroughly characterized by nuclear magnetic resonance (¹H‐NMR), Fourier transform infrared spectroscopy and X‐ray‐induced photoelectron spectroscopy. Additionally dynamic contact angle measurements are performed comparing the sinking rate of water droplets at different temperatures. The pH‐ and thermo‐double sensitivities of the modified membranes are proven by determining the water flux under different temperature and pH conditions.