Synthesis of PS colloidal crystal templates and ordered ZnO porous thin films by dip-drawing method

Polystyrene spheres (PS) were synthesized by an emulsifier-free emulsion polymerization technique and the PS colloidal crystal templates were assembled orderly on clean glass substrates by dip-drawing method from emulsion of PS. Porous ZnO thin films were prepared by filling the ZnO sol into the spaces among the close-packed PS templates and then annealing to remove the PS templates. The effects of ZnO precursor sol concentration and dipping time in sol on the porous structure of the thin films were studied. The results showed an ordered ZnO porous thin film with designed pore size that depended on the sol concentration and PS size could be obtained. And the shrinkage of pore diameter was about 30-43%. X-ray diffraction (XRD) spectra indicated the thin film was wurtzite structure. The transmittance spectrum showed that optical transmittance decreased with the decrease of wavelength, but kept above 80% optical transmittances beyond the wavelength of 550 nm. Optical band gap of the porous ZnO thin film (fired at 500 °C) was 3.22 eV.     

A simple method for the preparation of superhydrophobic PVDF-HMFS hybrid composite coatings

A superhydrophobic surface was obtained by embedding hydrophobically modified fumed silica (HMFS) particles in polyvinylidene fluoride (PVDF) matrix. The water contact angle (WCA) on the PVDF-HMFS hybrid composite coating is influenced by the content and nature of silica particles in the coating. As the silica concentration in PVDF matrix was increased from 33.3% to 71.4%, WCA increased from 117° to 168° and the sliding angle decreased from 90° to <1°. Surface topography of the coating was examined using scanning electron microscopy. An irregular rough surface structure composed of microcavities and nanofilaments was found to be responsible for the superhydrophobicity. The method is simple and cost-effective and can be used for preparing self-cleaning superhydrophobic coating on large areas of different substrates.     

Superhydrophobic poly(vinylidene fluoride) film fabricated by alkali treatment enhancing chemical bath deposition

Based on the lotus effect principle, the superhydrophobic poly(vinylidene fluoride) (PVDF) film was successfully prepared by the method of alkali treatment enhancing chemical bath deposition. The surface of PVDF film prepared in this work was constructed by many smooth and regular microreliefs. Oxygen-containing functional groups were introduced in PVDF film by treatment with aqueous NaOH solution. The nano-scale peaks on the top of the microreliefs were implemented by the reaction between dimethyldichlorosilane/methyltrichlorosilane solution and the oxygen-containing functional groups of PVDF film. The micro- and nano-scale structures, similar to the lotus leaf, was clearly observed on PVDF film surface by scanning electronic microscopy (SEM) and atomic force microscope (AFM). The water contact angle and sliding angle on the fabricated lotus-leaf-like PVDF film surface were 157° and 1°, respectively, exhibiting superhydrophobic property and self-cleaning property.     

Preparation of superhydrophobic membranes by electrospinning of fluorinated silane functionalized poly(vinylidene fluoride)

Fluorinated silane functionalized poly(vinylidene fluoride) (PVDF) is synthesized by graft polymerization of 3-trimethoxylpropyl methylacrylate with PVDF followed by coupling of fluorinated silanes. Flat membrane prepared using this functionalized PVDF has a water contact angle of 140°. Superhydrophobic PVDF membrane with a contact angle larger than 150° is prepared by the electrospinning of the fluorinated silane functionalized PVDF. The morphologies of the membranes are characterized using scanning electron microscopy. The surface composition of the membranes is analyzed using FTIR and the contact angles and water drops on the surface of the membrane are measured using video microscopy.     

Superhydrophobicity of polyvinylidene fluoride membrane fabricated by chemical vapor deposition from solution

Due to the chemical stability and flexibility, polyvinylidene fluoride (PVDF) membranes are widely used as the topcoat of architectural membrane structures, roof materials of vehicle, tent fabrics, and so on. Further modified PVDF membrane with superhydrophobic property may be even superior as the coating layer surface. The lotus flower is always considered to be a sacred plant, which can protect itself against water, dirt, and dust. The superhydrophobic surface of lotus leaf is rough, showing the micro- and nanometer scale morphology. In this work, the microreliefs of lotus leaf were mimicked using PVDF membrane and the nanometer scale peaks on the top of the microreliefs were obtained by the method of chemical vapor deposition from solution. The surface morphology of PVDF membrane was investigated by scanning electronic microscopy (SEM) and atomic force microscope (AFM). Elemental composition analysis by X-ray photoelectron spectroscopy (XPS) revealed that the material of the nanostructure of PVDF membrane was polymethylsiloxane. On the lotus-leaf-like PVDF membrane, the water contact angle and sliding angle were 155° and 4°, respectively, exhibiting superhydrophobic property.     

Preparation and electroactive properties of a PVDF/nano-TiO2 composite film

In the present study, poly(vinylidene fluoride) (PVDF)/nano-TiO₂ electroactive film was prepared by coating a substrate with an acetone/DMF solution, which was evaporated at a high temperature (110 °C). The crystallisation behaviour, dynamic mechanical properties and electroactive properties of this PVDF/nano-TiO₂ electroactive film were investigated. The cross-section and surface of the film were observed with a scanning electron microscope (SEM). X-ray diffraction (XRD) results showed that the film containing the PVDF β phase, the desired ferroelectric phase, was obtained by crystallising the mixed solution of nano-TiO₂ and PVDF at 110 °C, while the film containing the α phase was obtained from the crystallisation of the pure PVDF solution at the same temperature. It was found that the storage modulus, the room-temperature dielectric constant and the electric breakdown strength of the composite films were much higher than those of a pure PVDF film. TiO₂ improved the mechanical properties and electroactive properties of the film. The results indicate that PVDF/nano-TiO₂ composite films can be applied to the fabrication of self-sensing actuator devices.     

Fabrication of three-dimensionally ordered macroporous Ta2O5 films through aqueous organic gel process

Ta₂O₅ thin films have been prepared in the forms of three-dimensionally ordered macroporous (3-DOM) materials through aqueous organic gel process guided by polystyrene (PS) colloidal templates. The structure of the films was strongly affected by the infiltration process. This suggests that the infiltration process which aims at introducing desired materials into the interstitial spaces between the PS templates is of critical importance. Dip-drawing method was adopted for infiltration in this article. However, excess precursor worked as a capping agent for films prepared from the precursor of high concentration. Spin-coating method can efficiently remove the excess precursor by high speed rotating, which makes it a promising process for the infiltration of Ta-citric precursor with concentration higher than 0.5 mol/L. X-ray diffraction (XRD) pattern showed that the products can crystallize at 600 °C and had a pure orthorhombic phase. The chemical composition of the product was also studied by X-ray photoelectron spectroscopy (XPS).     

Gold nanostructures on chemically reinforced PDMS microwell arrays

This paper describes a facile strategy for fabricating arrays of two- and three-dimensional gold nanostructures using PDMS-infiltrated polystyrene (PS) colloidal crystals. PDMS molding of colloidal crystal, gold vapor deposition, and subsequent calcination of PS produced gold thin layers over hexagonal PDMS microwell arrays with hemispherical air-voids of approximately 140 nm on glass substrates. Vapor deposition of perfluoroalkylsilane thin layers improved the thermal stability of the colloidal template over 100 °C, providing a route to preparation of hollow architectures with gold thin layers supported by PDMS nanostructures. Surface modification of the PDMS using poly(allylamine hydrochloride) induced two-dimensional colloidal crystals of PS and PMMA spheres through electrostatic interactions. Particle aggregation of 13 nm gold nanoparticles in the PDMS microwells demonstrated a surface plasmon resonance band red-shifted to 810 nm, in comparison with that on the flat surface at 720 nm.     

Surface and interfacial properties of PVDF/acrylic copolymer blends before and after UV exposure

Morphological and chemical properties of both the surface and interface of poly(vinylidene fluoride)/poly(methyl methacrylate)-co-poly(ethyl acrylate) (PVDF/PMMA-co-PEA) blend films have been investigated before and after the samples were exposed to ultraviolet (UV) irradiation using a xenon arc lamp at 50 °C and 9% relative humidity (RH) for 7 months. Surface and interfacial morphologies were studied by atomic force microscopy (AFM). Chemical composition information was obtained by confocal Raman microscopy, attenuated total reflection-FTIR spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Results show an enrichment of the PVDF material at the air surface, while the acrylic copolymer enriches the interface. Blends having greater than 50% mass fraction of PVDF show little change in the surface morphology after UV exposure for 7 months. However, for a lower PVDF content, blends exhibit significant degradation of PMMA-co-PEA copolymer and a much rougher surface after UV exposure. Microstructural changes in the PVDF spherulites are also observed after UV degradation. It is found that the surface and interfacial morphologies are correlated with the chemical properties.     

Investigation of Polyvinylidene Fluoride Membranes Prepared by Using Surfactant OP-10 Alone or with a Second Component,as Additives,via the Non-Solvent-Induced Phase Separation (NIPS) Process

Polyvinylidene fluoride (PVDF) flat-sheet membranes were prepared via a non-solvent-induced phase separation (NIPS) method at 60°C using a hydrophilic surfactant OP-10 (octylphenol polyoxyethylene ether) solely (Blank) or with a second additive [H₂O or lithium chloride (LiCl)] as pore-forming agents. The influence of OP-10 concentration on the surface tension, viscosity, and precipitation rate of PVDF/(H₂O, LiCl, or Blank) systems were investigated, and the ultrafiltration and mechanical properties of the resultant membranes were measured. It was found that an increased demixing rate during the coagulation process was the reason for the change in membrane morphology and properties. An obviously improved flux and slightly decreased mechanical properties and rejection were found in membranes prepared using a high concentration of OP-10 and the second component as additives. SEM pictures revealed an increased porous structure on the resultant membrane surface. A hypothesis was proposed to explain these phenomena; the reoriented surfactant molecules at the interface facilitated the water diffusion channels, which finally became the porous structure on the membrane surface. The weakened mechanical properties were due to the macrovoid structure in its membrane cross-section, which developed from the micelle structure in the casting solution. This hypothesis was further confirmed in a PVDF/OP-10/polyethylene glycol (PEG) system. A consistent conclusion was obtained.     

Bilayer porous scaffold based on poly-(?-caprolactone) nanofibrous membrane and gelatin sponge for favoring cell proliferation

Electrospun poly-(?-caprolactone) (PCL) nanofibers has been widely used in the medical prosthesis. However, poor hydrophilicity and the lack of natural recognition sites for covalent cell-recognition signal molecules to promote cell attachment have limited its utility as tissue scaffolds. In this study, Bilayer porous scaffolds based on PCL electrospun membranes and gelatin (GE) sponges were fabricated through soft hydrolysis of PCL electrospun followed by grafting gelatin onto the fiber surface, through crosslinking and freeze drying treatment of additional gelatin coat and grafted gelatin surface. GE sponges were stably anchored on PCL membrane surface with the aid of grafted GE molecules. The morphologies of bilayer porous scaffolds were observed through SEM. The contact angle of the scaffolds was 0°, the mechanical properties of scaffolds were measured by tensile test, Young's moduli of PCL scaffolds before and after hydrolysis are 66–77.3 MPa and 62.3–75.4 MPa, respectively. Thus, the bilayer porous scaffolds showed excellent hydrophilic surface and desirable mechanical strength due to the soft hydrolysis and GE coat. The cell culture results showed that the adipose derived mesenchymal stem cells did more favor to adhere and grow on the bilayer porous scaffolds than on PCL electrospun membranes. The better cell affinity of the final bilayer scaffolds not only attributed to the surface chemistry but also the introduction of bilayer porous structure.     

Effect of surface fluorination on the photocatalytic and photo-induced hydrophilic properties of porous TiO2 films

Porous surface-fluorinated TiO₂ (F-TiO₂) films were prepared through PEG modified sol-gel method and surface fluorination. The as-prepared films were characterized with XRD, FTIR, AFM, XPS and UV-vis DRS. The effects of surface fluorination on the photocatalytic activity and hydrophilicity of porous TiO₂ film were studied by photocatalytic degradation of rhodamine B (RhB) as well as water contact angle (CA) on porous TiO₂ film. The results showed that the surface fluorination increased the adsorption of RhB on the porous TiO₂ film and enhanced the photocatalytic degradation of RhB. The concentration and pH of NaF solutions affected much the photocatalytic activity of porous TiO₂ film. Porous F-TiO₂ film prepared in 40 mM NaF solution at pH 4.0 showed the highest photocatalytic activity. Because of its porous structure, the porous F-TiO₂ film had original water CA of 22.7°, which is much smaller than that of normal F-TiO₂ film. Under UV light irradiation, the water CA of porous F-TiO₂ film decreased to 5.1° in 90 min.     

Annealing and amorphous silicon passivation of porous silicon with blue light emission

The photoluminescence (PL) of the annealed and amorphous silicon passivated porous silicon with blue emission has been investigated. The N-type and P-type porous silicon fabricated by electrochemical etching was annealed in the temperature range of 700-900 °C, and was coated with amorphous silicon formed in a plasma-enhanced chemical vapor deposition (PECVD) process. After annealing, the variation of PL intensity of N-type porous silicon was different from that of P-type porous silicon, depending on their structure. It was also found that during annealing at 900 °C, the coated amorphous silicon crystallized into polycrystalline silicon, which passivated the irradiative centers on the surface of porous silicon so as to increase the intensity of the blue emission.     

Applied electric field to fabricate colloidal crystals with the photonic band-gap in communication waveband

The macropore silica colloidal crystal templates were assembled orderly in a capillary glass tube by an applied electric field method to control silica deposition. In order to achieve the photonic band gap (PBG) of colloidal crystal in optical communication waveband, the diameter of silica microspheres is selected by Bragg diffraction formula. An experiment was designed to test the bandgap of the silica crystal templates. This paper discusses the formation process and the close-packed fashion of the silica colloidal crystal templates was discussed. The surface morphology of the templates was also analyzed. The results showed that the close-packed fashion of silica array templates was face-centered cubic (FCC) structure. The agreement is very good between the experimental data and the theoretical calculation.     

White light luminescence from annealed thin ZnO deposited porous silicon

In this study, photoluminescence (PL) properties of annealed ZnO thin films deposited onto a porous silicon (PS) surface by rf-sputtering were investigated. A huge blue shift of luminescence from the ZnO deposited onto the PS surface and a broadband luminescence (white luminescence) across most of the visible spectrum were obtained after the heat treatment at 950 °C in air. The results of Fourier Transform Infrared Spectroscopy (FTIR) analysis suggested that the porous silicon surface was oxidized after ZnO deposition and the broadband luminescence was due to the conversion of Si-H bonds to Si-O-Si bonds on the PS surface. The underlying mechanisms of the broadband PL were discussed by using oxygen-bonding model for the PS and native defects model for ZnO. The experimental results suggested that the heat treatment provides a relatively easy way to achieve white luminescence from thin ZnO deposited porous silicon.     

Silver nanorods used to promote SERS as a quantitative analytical tool

We have fabricated silver nanorod arrays by electrodepositing the nanorods evenly in the shallow pores of porous anodic aluminum oxide (AAO) templates. The diameter and length were 28 and 44 nm, respectively. The maxima of the transverse and longitudinal modes of the surface plasmon were near 417 and 511 nm, respectively. A good surface‐enhanced Raman scattering (SERS) spectrum was observed by excitation with the 514.5‐nm laser line. The SERS intensity increased almost linearly upon malachite green isothiocyanate adsorption on the tips of the silver nanorods as the concentration of the mother solutions increased. Our results show that silver nanorods fabricated on AAO templates could be used as an SERS substrate for quantitative analyses. Copyright © 2009 John Wiley & Sons, Ltd.     

聚苯乙烯多孔薄膜的密度梯度控制

利用单分散的SiO2微球自组装制备了含一种尺寸微球的SiO2胶体晶体和含多种尺寸微球的多层异质结构。对含一种尺寸微球的SiO2胶体晶体进行煅烧和刻蚀处理后,胶体晶体中空隙所占比例大于立方密堆结构的26%,形成了非密堆结构,而且刻蚀时间越长,空隙比例越大。在同样的热处理和刻蚀条件下,微球尺寸越小的胶体晶体被刻蚀的程度越高,结构中空气空隙所占的比例越大。对SiO2多层异质结构经过煅烧和刻蚀处理后,得到了空隙梯度变化的多层结构,以此为模板制备了密度梯度变化的聚苯乙烯多孔薄膜。薄膜各层之间形成了平滑的过渡,没有显示出明显的层间缺陷,且孔与孔之间没有出现3维有序多孔结构中常见的大的连通孔道。     

Non-chromate deoxidation of AA2024-T3: Sodium bromate-nitric acid (20-60 °C)

The effect of a non-chromate deoxidiser (bromate-nitric acid) on AA2024-T3 has been examined by SEM, TEM/EELS and XPS. At low temperatures (20 °C) the deoxidiser removed all intermetallics but had little effect on the surface oxide. At 40 °C, attack on the intermetallics was again extensive but there was also evidence of attack on the surface oxide covering the matrix after 10 min of immersion, leaving a roughened porous oxide. At 60 °C, removal of intermetallics was complete and longer immersion times resulted in a characteristic scalloped structure across the surface which became more pronounced with increasing immersion time.     

Fabrication of superhydrophobic surfaces on zinc substrates

Stable superhydrophobic surfaces were fabricated on the zinc substrates through simple silver replacement deposition process with the modification of octadecyl mercaptan. The effects of reaction conditions on the surface morphology and wettability of the prepared surfaces were carefully studied. The results show that the fabrication of a best superhydrophobic surface depends largely on the moderate reactant concentration. When the concentration of AgNO₃ solution was 2 mmol/L, the zinc substrate was covered by a dendritic outline structure. Aggregated silver nanoparticles were formed on the substrate in accordance with some certain laws, exhibiting great surface roughness. The typical hierarchical micro-nanostructures, flower-like structures and porous structures also could be found from the SEM images. The maximal water contact angle (CA) value of about 161 ± 2°, and the minimal sliding angle (SA) of about 2° were obtained under the same reaction condition.     

Conciliating surface superhydrophobicities and mechanical strength of porous silicon films

Hydrophobic surfaces on Mechanical stable macroporous silicon films were prepared by electrochemical etching with subsequent octadecyltrichlorosilane (OTS) modification. The surface morphologies were controlled by current densities and the mechanical properties were adjusted by their corresponding porosities. Contrast with the smooth macroporous silicon films with lower porosities (34.1%) and microporous silicon with higher porosities (97%), the macroporous film with a rough three-dimension (3D) surface and a moderate pore to cross-section area ratio (37.8%, PSi2′) exhibited both good mechanical strength (Yong’ modulus, shear modulus and collapse strength are 64.2, 24.1 and 0.32 GPa, respectively) and surface superhydrophobicity (water contact angle is 158.4 ± 2° and sliding angle is 2.7 ± 1°). This result revealed that the surface hydrophobicities (or the surface roughness) and mechanical strength of porous films could be conciliated by pore to cross-section area ratios control and 3D structures construction. Thus, the superhydrophobic surfaces on mechanical stable porous films could be obtained by 3D structures fabrication on porous film with proper pore to cross-section area ratios.