Coating of Methyltriethoxysilane—Modified Colloidal Silica on Polymer Substrates for Abrasion Resistance

Organic-inorganic hybrid composites were prepared by the sol-gel method for the hard coating agent of transparent plastic, and their abrasion resistance, optical and surface characteristics were evaluated. Methyltriethoxy-silane (MTES) and colloidal silica were used as starting materials. The addition of MTES to colloidal silica enabled the formation of dense thin films with very smooth surface on the substrates. The thin films were strongly adhered to the substrates without primer treatment. The abrasion resistance increased with the increase in the ratio of MTES to the colloidal silica. Optimal amount of MTES for the hard coating agent was 100 wt% to the colloidal silica. The addition of curing catalyst, tetramethylammonium formate was found to be very effective to enhance the adhesion strength of coating agent to the substrates and reduced curing time.     

Silica Films Containing Ordered Pores Prepared by Dip Coating of Silica Nanoparticles and Polystyrene Beads Colloidal Mixture

Silica films containing three dimensionally (3D) ordered pores were prepared by a simple dip coating method. A colloidal sol containing silica particles in the nanometer size range and a polystyrene latex (PSL) colloidal sol containing particles of tens of nanometers to one micrometer in size were used as precursors. The pore periodicity, which in turn produces the dielectric periodicity, can be easily altered by changing the size of the PSL beads. Films having a high surface smoothness were obtained by using small silica particles, large PSL particles, and a low withdrawal speed in the dip-coating. When the films were irradiated with a white light source, the reflective spectrum was changed by varying the incident angle, indicating its possible use as a monochromator. The change in the reflective spectrum was explained using effective medium approximation combined with a simple Bragg reflection equation.     

Superhydrophobic polyimide films with a hierarchical topography: combined replica molding and layer-by-layer assembly

Artificial superhydrophobic surfaces with a hierarchical topography were fabricated by using layer-by-layer assembly of polyelectrolytes and silica nanoparticles on microsphere-patterned polyimide precursor substrates followed with thermal and fluoroalkylsilane treatment. In this special hierarchical topography, micrometer-scale structures were provided by replica molding of polyamic acid using two-dimensional arrays of polystyrene latex spheres as templates, and nanosized silica particles were then assembled on these microspheres to construct finer structures at the nanoscale. Heat treatment was conducted to induce chemical cross-linking between polyelectrolytes and simultaneously convert polyamic acid to polyimide. After surface modification with fluoroalkylsilane, the as-prepared highly hydrophilic surface was endowed with superhydrophobicity due to the bioinspired combination of low surface energy materials and hierarchical surface structures. A superhydrophobic surface with a static water contact angle of 160 degrees and sliding angle of less than 10 degrees was obtained. Notably, the polyimide microspheres were integrated with the substrate and were mechanically stable. In addition, the chemical and mechanical stability of the polyelectrolyte/silica nanoparticle multilayers could be increased by heat-induced cross-linking between polyelectrolytes to form nylon-like films, as well as the formation of interfacial chemical bonds.     

聚苯乙烯胶晶膜及三维有序大孔SiO2膜的制备及表征

采用垂直沉积法组装了三维聚苯乙烯胶晶膜,并用其为模板制备了三维有序大孔（3DOM）SiO2膜．SEM观察表明,制备的胶晶膜和3DOMSiO2膜具有fcc结构,有序性很好．考察乳液浓度对胶晶膜结构的影响表明,浓度越高,胶晶膜越厚,有序性也越高,膜在30层内都能很好的粘附在载玻片上．通过调整前驱物溶液的浓度和滴加方式,可得到表面为球形或孔状的3DOM SiO2膜．     

SiO2胶体晶体垂直沉积自组装方法的改进

采用垂直沉积技术及相应的改进方法,使用化学合成的400 nm单分散二氧化硅微球自组装制备了胶体晶体薄膜。通过扫描电镜与分光光度计对样品的微观结构与透过光谱进行了表征,并对比研究了不同的垂直沉积方法对胶体晶体的影响。结果表明,通过温度与流量控制两种改进手段,均能制备具有六方密堆结构周期排列的胶体晶体薄膜。在垂直沉积过程中适当的升高温度有利于降低胶体粒子的用量,而通过流量控制的垂直沉积技术则可以有效缩短自组装时间。通过调节蠕动泵改变液面与基板的相对运动速度,或者调控温度改变胶体溶液的蒸发速率,可在材料表面形成单层或多层的胶体晶体薄膜。改进的垂直沉积技术将有望应用于快速沉积大面积、高质量的胶体晶体材料。     

Effect of anionic surfactants on synthesis and self-assembly of silica colloidal nanoparticles

Effects of the anionic surfactants, sodium dodecyl sulfate and sodium oleate, on the formation and properties of silica colloidal nanoparticles were investigated. At a concentration of approximately 1 x 10(-3) M, adsorption of anionic surfactants increased particle size, monodispersity, and negative surface charge density of synthesized silica particles. As uniformity of particle size and particle-particle interactions increase, colloidal photonic crystals readily self-assemble without extensive washing of the synthesized silica nanoparticles. The photonic crystals diffract light in the visible region according to Bragg's law. The assembled colloidal particle arrays exhibit a face-centered cubic structure in dried thin films. This study offers a new approach for producing ordered colloidal silica thin films.     

Ion transport in sulfonated nanoporous colloidal films

The surface of self-assembled nanoporous silica colloidal crystalline films comprised of 184-nm-diameter silica spheres has been sulfonated using 1,3-propanesultone. The transport of ions through the sulfonated films has been studied using cyclic voltammetry in water as a function of ion charge, pH, and solution ionic strength. We found that the flux of anions through the sulfonated colloidal films is reduced, while the flux of cations is increased, compared to the unmodified colloidal films. This behavior is pH-dependent and is due to electrostatic repulsion/attraction that can be modulated by changing the ionic strength of the contacting solution.     

大面积超疏水性纳米结构碳膜的制备与表征

利用一种简单的热解方法, 制备了具有纳米结构的大面积碳膜, 膜表面经过低表面能物质氟硅烷修饰后具有超疏水性.     

Fabrication of binary colloidal crystals and non-close-packed structures by a sequential self-assembly method

Binary colloidal films of polystyrene (PS) spheres and silica spheres were fabricated with a sequential growth method using differently sized colloidal particles. In particular, we demonstrate the structures formed by a silica monolayer growing on top of a PS monolayer and a silica multilayer growing on top of a PS monolayer. By removal of the bottom PS layers, non-close-packed hexagonal, pentagonal, and square silica arrays were obtained at the original silica/PS interface. The possible formation mechanism of the non-close-packed structure was discussed, which may be used to explain how 3D colloidal crystals grow on patterned substrates.     

Inward-growing self-assembly of colloidal crystal films on horizontal substrates

Colloidal crystal films have been fabricated on solid substrates with a horizontal deposition method. Scanning electron microscope images showed that the colloidal crystal films exhibit ordered face-centered cubic structures in large domains. Optical measurements demonstrated the presence of photonic band gap along the crystallographic [111] direction. The fabrication method described in this paper allows one to rapidly fabricate colloidal crystal films of different thicknesses, which can be controlled by varying colloidal suspension concentration or volume. In addition, the method also works well for growing colloidal crystal films on a hydrophilic solid substrate with a rough surface. Furthermore, the fabrication of colloidal crystal heterostructures has been demonstrated. An inward-growing mechanism responsible for self-assembly of colloidal spheres on horizontal substrates has been proposed to interpret the observed experimental results.     

Submicron scale patterning in sintered silica colloidal crystal films using a focused ion beam

Focused ion beam milling is used to fabricate micron and submicron scale patterns in sintered silica colloidal crystal films. Rectangular cavities with both solid and porous boundaries, fluidic channels, and isolation of a small number of packed spheres are patterned. The ion beam can pattern sintered films of individual submicron size spheres and create patterns that cover up to 40 mum in less than 15 min. The experiments in this work indicate that the amount of redeposited material on the surface of a milled cavity determines whether the surface will be porous or solid. FIB direct patterning has applications in colloidal crystal based lithography, integrated photonic devices, optofluidic devices, and micrototal-analytical systems.     

Characterization of Plasma Polymerized Hexamethyldisiloxane Films Prepared by Arc Discharge

Herein, we present a simple method for fabricating plasma polymerized hexamethyldisiloxane films (pp-HMDSO) possessing superhydrophobic characteristics via arc discharge. The pp-HMDSO films were deposited on a soda–lime–silica float glass using HMDSO monomer vapor as a precursor. A detailed surface characterization was performed using scanning electron microscopy and atomic force microscopy. The growth process of the pp-HMDSO films was investigated as a function of deposition time from 30 to 300 s. The non-wetting characteristics of the pp-HMDSO films were evaluated by means of contact angle (CA) measurements and correlated with the morphological characteristics, as obtained from microscopy measurements. The deposited films were found to be nano-structured and exhibited dual-scale roughness with the static CA values close to 170°. Fourier transform infrared spectroscopy analysis was carried out to investigate chemical and functional properties of these films. Methyl groups were identified spectroscopically to be present within the pp-HMDSO films and were proposed to result in the low surface energy of material. The synergy between the dual-scale roughness and low surface energy resulted in the superhydrophobic characteristics of the pp-HMDSO films. A possible mechanism for the pp-HMDSO film formation is proposed.     

Superhydrophobic bionic surfaces with hierarchical microsphere/SWCNT composite arrays

Superhydrophobic bionic surfaces with hierarchical micro/nano structures were synthesized by decorating single-walled or multiwalled carbon nanotubes (CNTs) on monolayer polystyrene colloidal crystals using a wet chemical self-assembly technique and subsequent surface treatment with a low surface-energy material of fluoroalkylsilane. The bionic surfaces are based on the regularly ordered colloidal crystals, and thus the surfaces have a uniform superhydrophobic property on the whole surface. Moreover, the wettability of the bionic surface can be well controlled by changing the distribution density of CNTs or the size of polystyrene microspheres. The morphologies of the synthesized bionic surfaces bear much resemblance to natural lotus leaves, and the wettability exhibited remarkable superhydrophobicity with a water contact angle of about 165 degrees and a sliding angle of 5 degrees.     

Inverse opal photonic crystal of chalcogenide glass by solution processing

Chalcogenide opal and inverse opal photonic crystals were successfully fabricated by low-cost and low-temperature solution-based process, which is well developed in polymer films processing. Highly ordered silica colloidal crystal films were successfully infilled with nano-colloidal solution of the high refractive index As(30)S(70) chalcogenide glass by using spin-coating method. The silica/As-S opal film was etched in HF acid to dissolve the silica opal template and fabricate the inverse opal As-S photonic crystal. Both, the infilled silica/As-S opal film (Δn ~ 0.84 near λ=770 nm) and the inverse opal As-S photonic structure (Δn ~ 1.26 near λ=660 nm) had significantly enhanced reflectivity values and wider photonic bandgaps in comparison with the silica opal film template (Δn ~ 0.434 near λ=600 nm). The key aspects of opal film preparation by spin-coating of nano-colloidal chalcogenide glass solution are discussed. The solution fabricated "inorganic polymer" opal and the inverse opal structures exceed photonic properties of silica or any organic polymer opal film. The fabricated photonic structures are proposed for designing novel flexible colloidal crystal laser devices, photonic waveguides and chemical sensors.     

Simple method for preparation of porous polyimide film with an ordered surface based on in situ self-assembly of polyamic acid and silica microspheres

In this Article, we addressed a facile method for the fabrication of porous polyimide film with an ordered surface based on the solvent-evaporation-assisted in situ self-assembly of polyamic acid (PAA, precursor of polyimide) and silica microspheres during vacuum-drying of PAA/silica colloid solution. Hydroxyl groups on the surface of silica microspheres have strong hydrogen-bonding with PAA chains, which improve the dispersion of silica microspheres in PAA/DMF solution and further help the self-assembly of PAA/silica colloid solution via solvent evaporation. The approach is simple, neither the preparation of special template nor complex preparation process and precise control over condition is necessary. Furthermore, the method could be employed for mass production of ordered porous polyimide films, and by changing the content and size of silica microspheres, the pore size and porous structure of the porous polyimide films could be tunable. The wettability behavior of the as-prepared porous polyimide films is also studied; the ordered surface topography of the porous polyimide films could change the wettability from hydrophilicity to hydrophobicity.     

Silica colloidal crystals as three-dimensional scaffolds for supported lipid films

This report describes the assembly of laterally diffusive lipid layers within the pores of colloidal crystals for potential application in membrane-based sensing. The amount of lipid encapsulated within colloidal crystals depends upon the method used to introduce the lipid to the crystalline substrate. Relative to a planar supported lipid bilayer, lipid loading in a 6.6 microm thick crystal was 15-73 times greater, as observed by fluorescence microscopy. Protein adsorption studies indicate that the crystal pores are open and that the silica surface of the crystal is passivated with respect to adsorption of a model protein when coated with POPC. Furthermore, the mesoporous environment of the colloidal crystal is found to protect lipid films from drying and rehydration processes that destroy planar supported lipid bilayers. The potential of colloidal crystal encapsulated lipid films for chemical sensing is demonstrated by a model protein binding assay.     

Aqueous dip-coating route to dense and porous silica thin films using silica nanocolloids with an aid of polyvinylpyrrolidone

An aqueous dip-coating route without using volatile alcohols for preparing dense and porous silica thin films is presented. The films were prepared by dip-coating on Si(100) and silica glass substrates using aqueous suspension of 8–11 nm colloidal silica where no alcohols were added. The addition of polyvinylpyrrolidone (PVP) in the suspension greatly improved the wettability, allowing homogeneous films to be formed on the substrates while the substrates showed poor wettability without PVP. When the as-deposited films were fired at 500–1,000 °C, optically transparent porous films with smooth surface were obtained. The porous films had homogeneous distribution and packing of silica nanoparticles, refractive indices of 1.24–1.33, and pencil hardness lower than 6B. The porous films underwent significant densification by viscous sintering when fired at temperatures over 1,000 °C. The viscous sintering was accompanied by the progress of condensation reaction and by the structural relaxation of siloxane network, which was revealed in the infrared absorption spectra. The resulting dense films had optical transparency, smooth surface, pencil hardness over 9H and refractive indices close to that of silica glass.     

Thin film formation of silica nanoparticle/lipid composite films at the fluid-fluid interface

We report a new and simple method for the formation of thin films at the interface between aqueous silica Ludox dispersions and lipid solutions in decane. The lipids used are stearic acid, stearyl amine, and stearyl alcohol alongside silica Ludox nanoparticle dispersions of varying pH. At basic pH thin films consisting of a mixture of stearic acid and silica nanoparticles precipitate at the interface. At acidic and neutral pH we were able to produce thin films consisting of stearyl amine and silica particles. The film growth was studied in situ with interfacial shear rheology. In addition to that, surface pressure isotherm and dynamic light scattering experiments were performed. The films all exhibit strong dynamic rheological moduli, rendering them an interesting material for applications such as capsule formation, surface coating, or as functional membranes.     

Asymmetric dimers can be formed by dewetting half-shells of gold deposited on the surfaces of spherical oxide colloids

Asymmetric dimers consisting of gold microcrystals and spherical silica colloids have been fabricated by depositing thin films of gold onto the spherical colloids to form half-shells, followed by annealing at elevated temperatures. The capability and feasibility of this procedure have been demonstrated with silica and titania beads of 0.2-2 mum in diameter and gamma-Fe2O3/polystyrene@SiO2 core-shell particles 0.5 mum in size. The dimensions of gold microcrystals could be conveniently varied in the range of 100-650 nm by controlling the thickness of gold films and/or the diameter of the spherical colloids. This method provides another route to asymmetric dimers made of colloidal particles that could be different in size, chemical composition, surface functionality, density or sign of surface charge, bulk property, or a combination of these properties.     

Colloidal interactions between Langmuir-Blodgett bitumen films and fine solid particles

In oil sand processing, accumulation of surface-active compounds at various interfaces imposes a significant impact on bitumen recovery and bitumen froth cleaning (i.e., froth treatment) by altering the interfacial properties and colloidal interactions among various oil sand components. In the present study, bitumen films were prepared at toluene/water interfaces using a Langmuir-Blodgett (LB) upstroke deposition technique. The surface of the prepared LB bitumen films was found to be hydrophobic, comprised of wormlike aggregates containing a relatively high content of oxygen, sulfur, and nitrogen, indicating an accumulation of surface-active compounds in the films. Using an atomic force microscope, colloidal interactions between the LB bitumen films and fine solids (model silica particles and clay particles chosen directly from an oil sand tailing stream) were measured in industrial plant process water and compared with those measured in simple electrolyte solutions of controlled pH and divalent cation concentrations. The results show a stronger long-range repulsive force and weaker adhesion force in solutions of higher pH and lower divalent cation concentration. In plant process water, a moderate long-range repulsive force and weak adhesion were measured despite its high electrolyte content. These findings provide more insight into the mechanisms of bitumen extraction and froth treatment.