New intelligent multifunctional SiO2/VO2 composite films with enhanced infrared light regulation performance,solar modulation capability,and superhydrophobicity

Abstract

Highly transparent, energy-saving, and superhydrophobic nanostructured SiO₂/VO₂ composite films have been fabricated using a sol–gel method. These composite films are composed of an underlying infrared (IR)-regulating VO₂ layer and a top protective layer that consists of SiO₂ nanoparticles. Experimental results showed that the composite structure could enhance the IR light regulation performance, solar modulation capability, and hydrophobicity of the pristine VO₂ layer. The transmittance of the composite films in visible region (T_lum) was higher than 60%, which was sufficient to meet the requirements of glass lighting. Compared with pristine VO₂ films and tungsten-doped VO₂ film, the near IR control capability of the composite films was enhanced by 13.9% and 22.1%, respectively, whereas their solar modulation capability was enhanced by 10.9% and 22.9%, respectively. The water contact angles of the SiO₂/VO₂ composite films were over 150°, indicating superhydrophobicity. The transparent superhydrophobic surface exhibited a high stability toward illumination as all the films retained their initial superhydrophobicity even after exposure to 365 nm light with an intensity of 160 mW^.cm^?2 for 10 h. In addition, the films possessed anti-oxidation and anti-acid properties. These characteristics are highly advantageous for intelligent windows or solar cell applications, given that they can provide surfaces with anti-fogging, rainproofing, and self-cleaning effects. Our technique offers a simple and low-cost solution to the development of stable and visible light transparent superhydrophobic surfaces for industrial applications.     

Enzyme biocatalyst route to superhydrophobic surfaces on microstructured poly(ethylene terephthalate) film

A tunable and green enzyme biocatalyst route to develop superhydrophobic surfaces on microstructured poly(ethylene terephthalate) (PET) films by the tailoring of the micro- and nano scale hierarchical structures is described. Upon the aminolysis of PET films with hexamethylenediamine, the primary amine groups are covalently attached onto the PET surfaces and microstructured pattern is formed. The binding of citrate-stabilized Au nanoparticles onto the PET surfaces via the covalent bond between the gold nanoparticles and the primary amine groups introduced on the PET surfaces was followed spectroscopically. The biocatalytic enlargement of the Au nanoparticles using the enzyme-generated H₂O₂ as reducing agent for the reduction of AuCl₄⁻ at the attached Au nanoparticle seeds on the PET surfaces was followed by spectroscopic means and atom force microscopy (AFM). The AFM experiments indicated that micro- and nano scale hierarchical structures were tailored by the enzyme biocatalyst route. Superhydrophobic surfaces with water contact angles as high as 158.6 ± 2.0° was achieved upon the chemisorption of 1-octadecanethiol as low surface energy material. This route can be potentially applicable to superhydrophobic PET-based microfluidic devices with reduced friction surfaces.     

仿生超疏水棉织物的制备与表面分析

以荷叶表面微/纳米结构为参考模型,先用硅溶胶处理天然棉织物,再用N-β-氨乙基-γ-氨丙基聚二甲基硅氧烷(ASO-1)对其进行修饰,获得了微/纳米二元粗糙的超疏水织物,水滴在该织物表面接触角可达160.5°。场发射扫描电子显微镜(FE-SEM)观察发现超疏水纤维表面存在大量均匀分布的纳米微凸体。接触角分析表明织物织造过程中形成的微米级粗糙度和ASO-1膜的存在是织物疏水的主要原因,纳米微凸体能减少纤维与水的接触面积,提高水在纤维表面的接触角,使织物由疏水转变为超疏水。最后用X射线光电子能谱仪(XPS)证实了纤维表面SiO2粒子和ASO-1膜的存在。     

Oxygen plasma treatment of SiOxCy(− H) films polymerized by atmospheric pressure dielectric barrier discharge using hexamethylcyclrotrisiloxane

The SiO₂-like layers were obtained by plasma-oxidation of the SiO_xC_y(− H) films deposited from hexamethylcyclotrisiloxane (HMCTSO) with helium and oxygen. The SiO₂-like layers were formed on as-deposited SiO_xC_y(− H) films within a second by oxidation using the He/O₂ atmospheric pressure dielectric barrier discharge (APDBD). The elemental ratio of oxygen to silicon in the layer was increased up to 1.95 which is closed to stoichiometry of SiO₂. The elemental composition and surface morphology were studied by means of x-ray photoelectron spectroscopy and atomic force microscopy. Wettability of the oxidized thin films was investigated by water droplet contact angle measurement. The contact angle of SiO_xC_y(− H) films are decreased from 63° to below 10° within a second by oxidation. Correlation between the elemental composition and the contact angle were discussed. The effects of oxidation duration and discharge generation voltage on the composition and surface morphology of the film were investigated.     

Robust Flower‐Like TiO2@Cotton Fabrics with Special Wettability for Effective Self‐Cleaning and Versatile Oil/Water Separation

Inspired by the hierarchical structure of the mastoid on the micrometer and nanometer scale and the waxy crystals of the mastoid on natural lotus surfaces, a facile one‐step hydrothermal strategy is developed to coat flower‐like hierarchical TiO₂ micro/nanoparticles onto cotton fabric substrates (TiO₂@Cotton). Furthermore, robust superhydrophobic TiO₂@Cotton surfaces are constructed by the combination of hierarchical structure creation and low surface energy material modification, which allows versatility for self‐cleaning, laundering durability, and oil/water separation. Compared with hydrophobic cotton fabric, the TiO₂@Cotton exhibits a superior antiwetting and self‐cleaning property with a contact angle (CA) lager than 160° and a sliding angle lower than 5°. The superhydrophobic TiO₂@Cotton shows excellent laundering durability against mechanical abrasion without an apparent reduction of the water contact angle. Moreover, the micro/nanoscale hierarchical structured cotton fabrics with special wettability are demonstrated to selectively collect oil from oil/water mixtures efficiently under various conditions (e.g., floating oil layer or underwater oil droplet or even oil/water mixtures). In addition, it is expected that this facile strategy can be widely used to construct multifunctional fabrics with excellent self‐cleaning, laundering durability, and oil/water separation. The work would also be helpful to design and develop new underwater superoleophobic/superoleophilic materials and microfluidic management devices.     

Investigation of superhydrophilic mechanism of titania nano layer thin film—Silica and indium oxide dopant effect

In this paper, TiO₂?CSiO₂?CIn₂O₃ nano layer thin films were deposited on glass substrate using sol?Cgel dip coating method. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and water contact angle measurements were used to evaluate chemical structure, surface composition, hydroxyl group contents and superhydrophilicity of titania films. FTIR result indicated that Si?CO?CSi, Si?CO?CTi and Ti?CO?CTi bands formed in TiO₂?CSiO₂?CIn₂O₃ sample. According to XPS, the hydroxyl content for TiO₂, TiO₂?CSiO₂ and TiO₂?CSiO₂?CIn₂O₃ films was calculated as 11·6, 17·1 and 20·7%, respectively. The water contact angle measurements indicated that silica and indium oxide dopant improved the superhydrophilicity of titania nano film surface especially in a dark place. The enhanced superhydrophilicity can be related to the generation of surface acidity on the titania nano film surfaces. In the present state, superhydrophilicity is induced by the simultaneous presence of both Lewis and Bronsted sites.     

Controlled growth of superhydrophobic films without any low-surface-energy modification by chemical displacement on zinc substrates

Superhydrophobic surface was prepared via immersing the clean perpendicular zinc substrate into aqueous copper (II) chloride (CuCl₂) solution and followed by anneal under the humid condition. The prepared samples were characterized by powder X-ray diffraction analysis, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy (XPS), and scanning electron microscopy (SEM), and energy-dispersive X-ray spectrometry analysis (EDX). SEM images of the films showed that the resulted surfaces exhibit micro–nano binary structures. The resulting surfaces had a high water contact angle (CA) of larger than 150° as well as a small sliding angle (SA) of less than 6°. Cu–Zn alloy formed by chemical displacement. Crystal CuZn₅ formed via crystal transition via anneal treatment. Crystal ZnO formed in air or under the humid condition. The CuZn₅–ZnO micro–nano binary structures leads to the surface superhydrophobicity.     

Weak acid–base interaction induced assembly for the formation of berry-like polystyrene/SiO2 composite particles

To investigate the formation mechanism of berry-like polystyrene/silica (PS/SiO₂) with carboxyl-functional templates through in-situ sol–gel process, different alkalis were adopted to catalyze the hydrolysis reaction of tetraethoxysilane (TEOS) and the morphology of composite particles was observed by TEM. The results showed that the weak acid–base interaction (–COO⁻/–N⁺/–SiO⁻) drove the silica particle nucleated and growth on the surface of PS spheres and berry-like structure can be easily adjusted by alkalis and volume ratio of ethanol/water. The present work implied that the weak acid–base interaction can be used to control the nano/micro or hierarchically structures. In addition, the particulate films were constructed by assembling these berry-like particles on the glass substrates. After surface modification with dodecyltrichlorosilane, hydrophobic surface can be obtained and the contact angle of water on the dual-sized structured surface can be adjusted.     

Fabrication and characterization of transparent superhydrophilic/superhydrophobic silica nanoparticulate thin films

The realization of transparent and superhydrophilic/superhydrophobic surfaces by silica nanoparticulate thin films was exploited in this work. An aqueous electrostatic layer-by-layer assembly process was utilized to fabricate nanoparticulate thin films with adhesion/body/top layer structure on glass substrates by using SiO₂ nanoparticles and polyelectrolytes. The effects of volume ratio of differently sized silica nanoparticle solutions for the body layer deposition on transmittance in visible light region and surface wettability of the nanoparticulate thin films were systematically studied. The experimental results revealed that both optical transparency and superhydrophobicity/superhydrophilicity can be achieved on the same SiO₂ nanoparticulate thin film by using appropriate volume ratios of differently sized silica nanoparticle solutions for body layer deposition, and with and without silane treatment in the fabrication process. The high contrast of wettability that can be achieved by this way suggests the possibility of the creation of superhydrophilic/superhydrophobic patterning and superhydrophilic-superhydrophobic gradient on the same surfaces.     

Free-standing functional graphene reinforced carbon films with excellent mechanical properties and superhydrophobic characteristic

In this work, we reported a simple method to fabricate novel free-standing stiff carbon-based composite films with excellent mechanical properties and superhydrophobic behaviors. The free-standing stiff carbon composite films based on reduced graphene oxide/glassy carbon (rGO/GC) were prepared by the combination of in-situ polymerization and carbonization process. The obtained composite films exhibited excellent mechanical properties by the addition of rGO nanosheets. It was found that incorporating 0.5 wt.% of rGO sheets in GC precursors resulted in enhancements of 99% in strength (202.6 MPa) and 184% in modulus (33.8 GPa), respectively. More interestingly, carbon nanoarrays were uniformly grown on the surface of composite films by the incorporation of rGO sheets. Superhydrophobic surfaces of carbon films were subsequently formed through functionalizing carbon nanoarrays with Trichloro(1H, 1H, 2H, 2H-perfluorodecyl)silane. Contact angle (CA) analysis suggested that superhydrophobic surfaces with a CA as high as 155° could be formed through optimizing the fabrication process.     

Composite SiOx/fluorocarbon plasma polymer films prepared by r.f. magnetron sputtering of SiO2 and PTFE

Composite films SiO_x/fluorocarbon plasma polymers were prepared by r.f. sputtering from two balanced magnetrons equipped with polytetrafluoroethylene (PTFE) and silica (SiO₂) targets. Argon was used as the working gas. The obtained films were characterised by means of XPS, RBS, FTIR, AFM, TEM, microhardness and static contact angle measurements. The obtained SiO_x/fluorocarbon plasma polymer films reveal different wettability (static contact angle of water ranges from 68° to 40°) and hardness (ranges from 720 to 3200 N/mm²) when the volume fraction ratio (filling factor) of SiO₂ changes from 0.01 to 0.7. The concentration of elements determined by RBS/ERDA varies strongly over this range of filling factors. The heterogeneous structure of the composite films is indicated by TEM at high SiO_x contents.     

Laser‐Induced Graphene in Controlled Atmospheres: From Superhydrophilic to Superhydrophobic Surfaces

The modification of graphene‐based materials is an important topic in the field of materials research. This study aims to expand the range of properties for laser‐induced graphene (LIG), specifically to tune the hydrophobicity and hydrophilicity of the LIG surfaces. While LIG is normally prepared in the air, here, using selected gas atmospheres, a large change in the water contact angle on the as‐prepared LIG surfaces has been observed, from 0° (superhydrophilic) when using O₂ or air, to >150° (superhydrophobic) when using Ar or H₂. Characterization of the newly derived surfaces shows that the different wetting properties are due to the surface morphology and chemical composition of the LIG. Applications of the superhydrophobic LIG are shown in oil/water separation as well as anti‐icing surfaces, while the versatility of the controlled atmosphere chamber fabrication method is demonstrated through the improved microsupercapacitor performance generated from LIG films prepared in an O₂ atmosphere.     

Superwetting Surfaces under Different Media: Effects of Surface Topography on Wettability

Superwetting surfaces in air, such as superhydrophobic and superoleophobic surfaces that are governed by surface chemical compositions and surface topographies, are one of the most extensively studied topics in this field. However, it is not well‐understood how surface topographies affect the behaviors of immiscible liquids and gases under other kinds of media, although it is significant in diverse fields. The main aim of this work is to systematically investigate the wetting behaviors of liquids (water and oil) and gas (air) on silicon surfaces with different topographies (i.e., smooth, micro, nano, and micro‐/nanostructures) under various media (i.e., air, water, and oil). The contact angles, as well as contact‐angle hysteresis, sliding angles, and adhesive forces, were utilized to evaluate the wettability of these surfaces. As a result, the microstructured surfaces typically exhibit high contact‐angle hysteresis, high sliding angles, and high adhesive forces, whereas the micro‐/nanostructured surfaces display low contact‐angle hysteresis, low sliding angles, and low adhesive forces, even if they have high (>150°) and similar contact angles. Furthermore, when transferring the same surface from one kind of medium to another, different superwetting states can be reversibly switched.     

Fabrication of high conductivity dual multi-porous poly (l-lactic acid)/polypyrrole composite micro/nanofiber film

Dual multi-porous PLLA (poly(l-lactic acid))/H₂SO₄-doped PPy (polypyrrole) composite micro/nano fiber films were fabricated by combining electrospinning with in situ polymerization. The morphologies and structures of the resulting samples were analyzed by scanning electron microscopy (SEM). It was found that the composite micro/nano fibers exhibited a core-shell structure and the composite fiber film had a dual multi-pore structure composed of pores both in the fibers and among the fibers. Semiconductor parameter analyzer was used to characterize the electrical properties of the samples. It was interesting to find that all the PLLA/H₂SO₄-doped PPy composite micro/nano fiber films had higher conductivity than H₂SO₄-doped PPy particles when the polymerization time up to 180 min. Effects of the pyrrole synthesis conditions on the pore size and the conductivity of PLLA/PPy composite fiber film were assessed. By optimizing the polymerization conditions, the max conductivity of this composite fiber film was about 179.0 S cm⁻¹ with a pore size of about 250 μm. The possible mechanism of PLLA/H₂SO₄-doped PPy composite micro/nano fiber films had much higher conductivity than H₂SO₄-doped PPy particles was discussed.     

Fabrication of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> double layer thin films with self-cleaning and photocatalytic properties

Transparent antireflective SiO₂/TiO₂ double layer thin films were prepared using a sol–gel method and deposited on glass substrate by spin coating technique. Thin films were characterized using XRD, FE-SEM, AFM, UV–Vis spectroscopy and water contact angle measurements. XRD analysis reveals that the existence of pure anatase phase TiO₂ crystallites in the thin films. FE-SEM analysis confirms the homogeneous dispersion of TiO₂ on SiO₂ layer. Water contact angle on the thin films was measured by a contact angle analyzer under UV light irradiation. The photocatalytic performance of the TiO₂ and SiO₂/TiO₂ thin films was studied by the degradation of methylene blue under UV irradiation. The effect of an intermediate SiO₂ layer on the photocatalytic performance of TiO₂ thin films was examined. SiO₂/TiO₂ double layer thin films showed enhanced photocatalytic activity towards methylene blue dye.     

疏水二氧化硅/聚苯乙烯超疏水复合涂层的简易制备及其防沾污性研究

采用喷枪及家用简易喷雾器在含有聚乙烯(PE)膜的纸张表面制备了含疏水二氧化硅纳米颗粒和聚苯乙烯的超疏水复合涂层。随着疏水二氧化硅纳米颗粒含量的增加,表面逐渐被二氧化硅颗粒覆盖,并且形成微纳米孔洞结构,达到超疏水性,并具有良好的耐粘附稳定性,水、牛奶和橙汁等液滴可从这些超疏水表面滚落而不残留,具有良好的防沾污能力。     

Facile preparation of superhydrophobic surface with high adhesive forces based carbon/silica composite films

Glass substrates modified by carbon/silica composites are fabricated through a two-step process for the preparation of a superhydrophobic surface (water contact angle ≥ 150°). Carbon nanoparticles were first prepared through a deposition process on glass using a hydrothermal synthesis route, then the glass was modified by SiO₂ using the hydrolysis reaction of tetraethylorthosilicate at room temperature. It is not only a facile method to create a superhydrophobic surface, but also helps to form a multi-functional surface with high adhesive forces.     

An investigation of super-hydrophilic properties of TiO2/SnO2 nano composite thin films

A sol-gel dip coating technique was used to fabricate TiO₂/SnO₂ nano composite thin films on soda-lime glass. The solutions of SnO₂ and TiO₂ were mixed with different molar ratios of SnO₂:TiO₂ as 0, 3, 4, 6, 8, 9, 10.5, 13, 15, 19.5, 25 and 28 mol.% then the films were prepared by dip coating of the glasses. The effects of SnO₂ concentration, number of coating cycles and annealing temperature on the hydrophilicity of films were studied using contact angle measurement. The films were characterized by means of scanning electron microscopy, X-ray diffraction and atomic force microscopy measurements. The nano composite thin films fabricated with 8 mol.% of SnO₂, four dip coating cycles and annealing temperature of 500 °C showed super-hydrophilicity.     

仿生超疏水聚丙烯/二氧化钛复合薄膜的构筑及性能研究

采用简便的相分离法制备出超疏水PP/TiO2复合薄膜。该复合薄膜表面与水的接触角为169°,滚动角小于4°。pH值为1~14的水溶液在其表面都具有很高的接触角,均大于160°。对其表面进行扫描电子显微镜分析可知,该薄膜具有类花瓣二元微纳米复合微观结构,这种结构可捕获空气,形成水与基底之间的气垫,对表面超疏水性的产生起到了关键作用。用Cassie理论对其表面超疏水进行分析,结果表明,约2.7%的面积是水滴和基体接触,而有约97.3%的面积是水滴和空气接触。     

Poly(dimethylsiloxane)-polyimide blends in the formation of thick polyimide films

Thick polyimide layers can be formed by using some unique properties of poly(dimethylsiloxane)-polyimide (PDMS/PMDA–ODA) blends followed by surface modification and deposition of a second layer of polyimide precursor chemicals. The method is based on the micro-phase separation characteristics of these blends to yield surfaces that have PDMS-like character. Upon modification with UV/ozone treatment, a surface that is essentially SiO _x and hydrophilic in nature is produced. This surface is amenable to reaction and deposition of a second polyimide layer from polyimide precursors. The thicker polyimide layer has enhanced adhesion between the original layer of the blend and the new polyimide layer and this approach finds extensive applications for products that require thick polymer layers. Changes in surface energy for various blend compositions were monitored by measurement of advancing contact angle with de-ionized water. Contact angle for unmodified polyimide films was on the order of 70° and it increased to about 104° after blending with PDMS and curing. UV/ozone treatment reduced the contact angle of the doped polyimide to less than 5°. X-ray photoelectron spectroscopy (XPS) and angle resolved XPS (ARXPS) measurements were used to monitor the chemical compositions of the various surfaces. High-resolution XPS spectra in the Si2p region confirm the transformation of O–Si–C bonds in PDMS to SiO _x , where x is about 2. Scanning electron microscopy (SEM) of some selected samples shows that the blends contain phase separation of the polymers at the surfaces of the samples. Atomic force microscopy (AFM) of siloxane-free polyimide, and PDMS/PMDA–ODA blends both prior to and after UV/ozone exposure, show that the films are essentially flat at short treatment times (less than 60 min). AFM also reveals the separation of PDMS into micro-domains at the cured film surface and throughout the layer below the surface of the blended films. Adhesion of a subsequently deposited polyimide layer to the modified polyimide surface was found to be greatly improved when compared to the adhesion obtained for deposition onto a pristine polyimide surface.