Dingcai Wu,*,† Fei Xu,† Bin Sun,† Ruowen Fu,† Hongkun He,‡ and Krzysztof Matyjaszewski*,‡ †Materials Science Institute, Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, People's Republic of China ‡Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States

Design and Preparation of Porous Polymers

This chapter highlights a variety of techniques that are commonly used to measure contact angles, including the conventional telescope-goniometer method, the Wilhelmy balance method, and the more recently developed drop-shape analysis methods. The various applications and limitations of these techniques are described. Notably, studies of ultrasmall droplets on solid surfaces allow wetting theories to be tested down to the nanometer scale, bringing new insight to contact angle phenomena and wetting behavior.

https://www.springer.com/cda/content/document/cda_downloaddocument/9783642342424-c1.pdf?SGWID=0-0-45-1368817-p174704744

Contact Angle and Wetting Properties

Design, and Applications Shutao Wang,†,‡ Kesong Liu, Xi Yao, and Lei Jiang*,†,‡,§ †Laboratory of Bio-inspired Smart Interface Science, Technical Institute of Physics and Chemistry, and ‡Beijing National Laboratory for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry and Environment, BeiHang University, Beijing 100191, People’s Republic of China Department of Biomedical Sciences, City University of Hong Kong, Hong Kong P6903, People’s Republic of China

Bioinspired Surfaces with Superwettability: New Insight on Theory, Design, and Applications

Removal of hazardous organics from water using metal-organic frameworks (MOFs): plausible mechanisms for selective adsorptions.

Fogging occurs when moisture condensation takes the form of accumulated droplets with diameters larger than 190 nm or half of the shortest wavelength (380 nm) of visible light. This problem may be effectively addressed by changing the affinity of a material’s surface for water, which can be accomplished via two approaches: i) the superhydrophilic approach, with a water contact angle (CA) less than 5°, and ii) the superhydrophobic approach, with a water CA greater than 150°, and extremely low CA hysteresis. To date, all techniques reported belong to the former category, as they are intended for applications in optical transparent coatings. A well-known example is the use of photocatalytic TiO2 nanoparticle coatings that become superhydrophilic under UV irradiation. Very recently, a capillary effect was skillfully adopted to achieve superhydrophilic properties by constructing 3D nanoporous structures from layer-by-layer assembled nanoparticles. The key to these two “wet”-style antifogging strategies is for micrometer-sized fog drops to rapidly spread into a uniform thin film, which can prevent light scattering and reflection from nucleated droplets. Optical transparency is not an intrinsic property of antifogging coatings even though recently developed antifogging coatings are almost transparent, and the transparency could be achieved by further tuning the nanoparticle size and film thickness. To our knowledge, the antifogging coatings may also be applied to many fields that do not require optical transparency, including, for example, paints for inhibiting swelling and peeling issues and metal surfaces for preventing corrosion. These types of issues, which are caused by adsorption of moisture, are hard to solve by the superhydrophilic approach because of its inherently “wet” nature. Thus, a “dry”-style antifogging strategy, which consists of a novel superhydrophobic technique that can prevent moisture or microscale fog drops from nucleating on a surface, is desired. Recent bionic researches have revealed that the self-cleaning ability of lotus leaves and the striking ability of a water-strider’s legs to walk on water can be attributed to the ideal superhydrophobicity of their surfaces, induced by special microand nanostructures. To date, the biomimetic fabrication of superhydrophobic microand/or nanostructures has attracted considerable interest, and these types of materials can be used for such applications as self-cleaning coatings and stain-resistant textiles. Although a superhydrophobic technique inspired by lotus leaves is expected to be able to solve such fogging problems because the water droplets can not remain on the surface, there are no reports of such antifogging coatings. Very recently, researchers from General Motors have reported that the surfaces of lotus leaves become wet with moisture because the size of the fog drops are at the microscale—so small that they can be easily trapped in the interspaces among micropapillae. Thus, lotuslike surface microstructures are unsuitable for superhydrophobic antifogging coatings, and a new inspiration from nature is desired for solving this problem. In this communication, we report a novel, biological, superhydrophobic antifogging strategy. It was found that the compound eyes of the mosquito C. pipiens possess ideal superhydrophobic properties that provide an effective protective mechanism for maintaining clear vision in a humid habitat. Our research indicates that this unique property is attributed to the smart design of elaborate microand nanostructures: hexagonally non-close-packed (ncp) nipples at the nanoscale prevent microscale fog drops from condensing on the ommatidia surface, and hexagonally close-packed (hcp) ommatidia at the microscale could efficiently prevent fog drops from being trapped in the voids between the ommatidia. We also fabricated artificial compound eyes by using soft lithography and investigated the effects of microand nanostructures on the surface hydrophobicity. These findings could be used to develop novel superhydrophobic antifogging coatings in the near future. It is known that mosquitoes possess excellent vision, which they exploit to locate various resources such as mates, hosts, and resting sites in a watery and dim habitat. To better understand such remarkable abilities, we first investigated the interaction between moisture and the eye surface. An ultrasonic humidifier was used to regulate the relative humidity of the atmosphere and mimic a mist composed of numerous tiny water droplets with diameters less than 10 lm. As the fog was C O M M U N IC A IO N

The dry-style antifogging properties of mosquito compound eyes and artificial analogues prepared by soft lithography: a superhydrophobic state with high adhesive force

In this study, we developed a facile method for preparing a superhydrophobic paper surface using a multi-layer deposition of polydiallyldimethylammonium chloride (polyDADMAC) and silica particles, followed by a fluorination surface treatment with 1H,1H,2H,2H-perfluorooctyltriethoxysilane (POTS, CF3(CF2)5CH2CH2Si(OC2H5)3). The superhydrophobic wood fiber products prepared in this study have contact angles of water greater than 150° and sliding angles less than 5°. Besides their high water repelling property, the superhydrophobic paper products kept a high tensile strength at high relative humidity condition. The superhydrophobic paper products also showed high resistance to bacterial contamination.

Preparation and physical properties of superhydrophobic papers

This article reports a simple, roll-to-roll compatible coating technology for producing 3D highly ordered colloidal crystal-polymer nanocomposites, colloidal crystals, and macroporous polymer membranes. A vertically beveled doctor blade is utilized to shear align silica microsphere-monomer suspensions to form large-area nanocomposites in a single step. The polymer matrix and the silica microspheres can be selectively removed to create colloidal crystals and self-standing macroporous polymer membranes. The thickness of the shear-aligned crystal is correlated with the viscosity of the colloidal suspension, and the coating speed and the correlations can be qualitatively explained by adapting the mechanisms developed for conventional doctor blade coating. We further demonstrate that the doctor blade coating speed can be significantly increased by using a dual-blade setup. The optical properties of the self-assembled structures are evaluated by normal-incidence reflection measurements, and the experimental results agree well with the theoretical predictions using Bragg's law and a scalar wave approximation model. We have also demonstrated that the templated macroporous polymers with interconnected voids and uniform interconnecting nanopores can be directly used as filtration membranes to achieve size-exclusive separation of particles.

Large-scale colloidal self-assembly by doctor blade coating.

Removing oil droplets from water using a copper-based metal organic frameworks

Diclofenac represents one of the most common pharmaceuticals and personal care products (PPCPs) in municipal wastewater. To enhance the removal of diclofenac from water, a cationic surfactant, cetyltrimethylammonium bromide (CTAB), was introduced into a zeolitic imidazole framework (ZIF)-67. CTAB is added originally to minimize the use of ligands during the synthesis of ZIF-67; however CTAB present in ZIF-67 also increases the surface charge and thus enhances the adsorption capacity up to 10 times compared to CTAB-free ZIF-67. Factors influencing the diclofenac adsorption are investigated, including CTAB loading, temperature and pH. A loading of 0.274 mol-CTAB/mol-Co2+ is suggested as an optimal loading to prepare a relatively efficient CTAB-ZIF-67, while over loading of CTAB could not fully incorporate CTAB into ZIF-67. In view of the diclofenac adsorption kinetics and isotherm, the adsorption of diclofenac to CTAB-ZIF-67 was considered to involve a strong affinity between diclofenac and CTAB-ZIF-67 owing to the electrostatic attraction between the carboxylic acid of diclofenac and the quaternary amine of CTAB. Considering that the removal of diclofenac from urine is of great interest, separation of diclofenac from urine using CTAB-ZIF-67 was evaluated and also employed to investigate the effect of co-existing ions. We also determined the desorption behavior of diclofenac from CTAB-ZIF-67 to provide insight for the recyclability of CTAB-ZIF-67 for diclofenac adsorption.

Enhanced removal of diclofenac from water using a zeolitic imidazole framework functionalized with cetyltrimethylammonium bromide (CTAB)

The cicada has transparent wings with remarkable self-cleaning properties and high transmittance over the whole visible spectral range, which is derived from periodic conical structures covering the wing surface. Here we report a scalable self-assembly technique for fabricating multifunctional optical coatings that mimic cicada-wing structures. Spin-coated two-dimensional non-close-packed colloidal crystals are utilized as etching masks to pattern subwavelength-structured cone arrays directly on polymer substrates. The resulting gratings exhibit broadband antireflection performance and superhydrophobic properties after surface modification. The dependence of the cone shape and size on the antireflective and self-cleaning properties has also been investigated in this study.

Hongta Yang

Papers

Preparation and physical properties of superhydrophobic papers

Large-scale colloidal self-assembly by doctor blade coating.

Removing oil droplets from water using a copper-based metal organic frameworks

Enhanced removal of diclofenac from water using a zeolitic imidazole framework functionalized with cetyltrimethylammonium bromide (CTAB)

Cicada-Wing-Inspired Self-Cleaning Antireflection Coatings on Polymer Substrates.