含罗丹明B的纳米复合介孔薄膜的制备和性能(英文)

采用溶胶-凝胶技术、蒸发诱导自组装法,通过酸/酸二步法控制实验条件,实验中采用表面活性剂十六烷基三甲基溴化氨(CTAB)为模板剂,正硅酸乙酯为硅源、罗丹明B、以及二次去离子水,盐酸为催化剂等原料制备前驱体溶胶.通过简单提拉迅速蒸发溶剂制备介孔薄膜,对介孔薄膜进行了X射线衍射、透射电子显微镜表征,观察了薄膜样品的吸收光谱和荧光光谱.含罗丹明B膜的吸收光谱表明主峰是RhB单体的吸收和微弱吸收的次峰是RhB形成的二聚体的吸收.而在荧光光谱中只有一个发射谱带,这是RhB单体的最低激发能级到基态级的跃迁,含罗丹明B的纳米复合介孔薄膜中,随着RhB浓度的增大,荧光峰位发生红移,这可以说明激发态分子的偶极矩减小.     

Spectroscopic studies and evanescent optical fibre wave sensing of Cu<Superscript>2+</Superscript> based on activated mesostructured silica matrix

This paper report on the synthesis and test of eriochrome cyanine R (ECR) doped mesostructured silica films as Cu²⁺ sensing without prior removal of the surfactant. ECR activated mesostructured silica (via sol-gel technique) coated optical fibre core were used to Cu²⁺ sensing by evanescent wave method. The sol was prepared via acidic hydrolysis-condensation of tetraethoxysilane (TEOS) in the presence of cetyltrimethylammonium bromide (CTAB:C₁₆H₃₃NCH₃Br) as the structure-directing agent. Spectrophotometric investigations using doped sol-gel thin films dip-coated on glass slides were reported. Heat treatment temperature effect (optimum temperature 150°C), absorption dependence on the pH of the aqueous phase (pH = 8 seems to be the optimal absorption pH), sensitivity, reversibility and response range (0.05 mmol/l) were reported.     

Study of mixed micelles and interaction parameters for polymeric nonionic and normal surfactants

Surface tension (ST) measurements were carried out on various binary mixtures of the "normal" surfactants, such as nonionic surfactant, hexaethylene glycol mono-n-dodecyl ether(C12EO6), and cationic surfactant, tetradecyltrimethylammonium bromide (TTAB), and polymeric copolymer, Pluronic F127, F127(PPO)-g-PVP, and F127(PEO)-g-PVP. In all cases mixed micellar aggregates were formed and critical micellar concentrations of binary mixtures containing different mole fractions of the surfactants were measured using surface tension measurement. In the region where mixed micelles are formed, the interaction of two "normal" surfactants and three "polymeric" nonionic surfactants showed synergistic behavior and the results were analyzed using a interaction parameter, beta, which characterized the interaction in the mixed micelle and introduced by a regular solution theory. The regular solution theory can be applied to describe the interaction between TTAB and C12EO6, and graft polymeric surfactants systems. The results discussed in this paper indicated that regular solution theory has broader extent of application.     

Electrochemically assisted self-assembly of mesoporous silica thin films

Supported mesostructured thin films are of major importance for applications in optical, electrochemical and sensing devices. However, good performance is restricted to mesostructured phases ensuring good accessibility from the film surface, which would be straightforward with cylindrical pores oriented normal to the underlying support, but this remains challenging. Here, we demonstrate that electrochemistry is likely to induce self-assembly of surfactant-templated (organo)silica thin films on various conducting supports, homogeneously over wide areas. The method involves the application of a suitable cathodic potential to an electrode immersed in a surfactant-containing hydrolysed sol solution to generate the hydroxyl ions that are necessary to catalyse polycondensation of the precursors and self-assembly of hexagonally packed one-dimensional channels that grow perpendicularly to the electrode surface. The method is compatible with controlled and localized deposition on heterogeneous supports, opening the way to electrochemically driven nanolithography for designing complex patterns of widely accessible mesostructured materials.     

微米α-Al_2O_3粉体的细化及其悬浮液的分散稳定性

在微米α-Al2O3粉体悬浮液中分别加入无机电解质类分散剂六偏磷酸钠、阳离子型表面活性剂十六烷基三甲基氯化铵、阴离子型表面活性剂油酸和非离子型表面活性剂异丙醇胺,并对悬浮液进行球磨分散,研究分散剂加球磨复合分散下的最优分散剂及最佳球磨参数;引入超声分散,对比分析在加入分散剂的情况下,先球磨再超声和只进行球磨时的分散效果。结果表明,采用十六烷基三甲基氯化铵为分散剂,先球磨2 h再超声分散15 min的分散效果最好,沉降24 h后的悬浮率为62%左右,平均粒径为243 nm。     

Solubilization of pyrene by anionic-nonionic mixed surfactants

Surfactant-enhanced remediation (SER) is an effective approach for the removal of sorbed hydrophobic organic compounds from contaminated soils. The solubilization of pyrene by four anionic-nonionic mixed surfactants, sodium dodecyl sulfate (SDS) with Triton X-405 (TX405), Brij35, Brij58, and Triton X-100 (TX100), has been studied from measurements of the molar solubilization ratio (MSR), the micelle-water partition coefficient (Kmc), and the critical micelle concentration (CMC). The MSRs of pyrene in mixed surfactants are found to be larger than those predicted according to an ideal mixing rule. The mixing effect of anionic and nonionic surfactants on MSR for pyrene follows the order of SDS-TX405 > SDS-Brij35 > SDS-Brij58 > SDS-TX100 and increases with an increase in the hydrophile-lipophile balance (HLB) value of nonionic surfactant in mixed systems. In addition, the mixture of anionic and nonionic surfactants cause the Kmc value for pyrene to be greater than the ideal value in SDS-TX405 mixed system, but to be smaller than the ideal value in SDS-Brij35, SDS-Brij58, and SDS-TX100 mixed systems. Meanwhile, in the four mixed systems, the experimental CMCs are lower than the ideal CMCs at almost all mixed surfactant solution compositions. The mixing effect of anionic and nonionic surfactants on MSR for pyrene can be attributed to the conjunct or the net result of the negative deviation of the CMCs from ideal mixture and the increasing or decreasing Kmc.     

The Adsorption of Mixed Surfactants at the Hydrophilic Silica Surface from Aqueous Solution: Studied by Specular Neutron Reflection

Specular neutron reflection has been used to determine the structure and composition of the mixed ionic–non-ionic surfactants adsorbed at the hydrophilic silica solid/water interface. Measurements on two different mixed surfactant systems are reported: the cationic/nonionic mixture of hexadecyltrimethyl ammonium bromide, C₁₆TAB, and hexaethylene glycol monododecyl ether, C₁₂E₆, and the anionic/nonionic mixture of sodium dodecyl sulfate, and C₁₂E₆. For the C₁₆TAB–C₁₂E₆ mixture, pH is shown to have a dramatic effect on the relative affinity for adsorption of the two surfactants at the interface.     

单分散短棒状介孔二氧化硅的制备

在温和碱性条件下,以十六烷基三甲基溴化铵为模板剂,正硅酸乙酯为硅源,平平加Os-25为助剂,制备出轴向尺寸为200nm左右,径向尺寸在60-80nm范围内的单分散短棒状纳米介孔二氧化硅MCM-41．研究了CTAB用量、平平加Os-25的用量、反应时间等因素对介孔形貌和纳米粒子分散性的影响．结果表明,适量的非离子表面活性剂平平加Os-25具有助模板剂的作用,可以有效地提高纳米介孔粉体的有序性．平平加Os-25与十六烷基三甲基溴化铵的摩尔比在0．02-0．06范围内,可以得到有序性好、分散性好的短棒状介孔二氧化硅MCM-41．     

Synthesis of nanocrystalline photocatalytic TiO2 thin films and particles using sol–gel method modified with nonionic surfactants

A simple sol–gel route has been developed for the preparation of nanocrystalline photocatalytic TiO₂ thin films and particles at 500 °C. The synthesis involved a novel chemistry method employing nonionic surfactant molecules as a pore directing agent along with acetic acid-based sol–gel route without direct addition of water molecules. This study investigated the effect of surfactant type and concentration on the homogeneity, morphology, light absorption, dye adsorption and degradation, and hydrophilicity of TiO₂ films as well as on the structural properties of the corresponding TiO₂ particles. The method resulted in the synthesis of mesoporous TiO₂ material with enhanced structural and catalytic properties including high surface area, large pore volume, pore size controllability, small crystallite size, enhanced crystallinity, and active anatase crystal phase. The prepared TiO₂ thin films were super-hydrophilic and possessed thermally stable spherical bicontinuous mesopore structure with highly interconnected network. Highly porous TiO₂ films prepared with polyethylene glycol sorbitan monooleate surfactant exhibited four times higher photocatalytic activity for the decoloration of methylene blue dye than the nonporous control TiO₂ films prepared without the surfactant. This sol–gel method modified with surfactant templates is useful in the preparation of nanostructured anatase TiO₂ thin films with high photocatalytic activity and desired pore structure.     

Highly textural lamellar mesostructured magnesium hydroxide via a cathodic electrodeposition process

Highly textural lamellar mesostructured Mg(OH)₂ thin films were obtained through one-step cathodic reduction of magnesium nitrate bath without any surfactant template at room temperature. Its microstructure, stability and morphology were investigated using XRD, TEM, FT-IR, thermal analysis and SEM technique respectively. The results indicate that the porous hydroxide/oxide materials have highly textural lamellar structures with layer spacing around 3.4 nm. The possible formation mechanism has been discussed.     

Surface deposition and phase behavior of oppositely charged polyion-surfactant ion complexes. Delivery of silicone oil emulsions to hydrophobic and hydrophilic surfaces

The adsorption from mixed polyelectrolyte-surfactant solutions at hydrophobized silica surfaces was investigated by in situ null-ellipsometry, and compared to similar measurements for hydrophilic silica surfaces. Three synthetic cationic copolymers of varying hydrophobicity and one cationic hydroxyethyl cellulose were compared in mixtures with the anionic surfactant sodium dodecylsulfate (SDS) in the absence or presence of a dilute silicone oil emulsion. The adsorption behavior was mapped while stepwise increasing the concentration of SDS to a polyelectrolyte solution of constant concentration. The effect on the deposition of dilution of the bulk solution in contact with the surface was also investigated by gradual replacement of the bulk solution with 1 mM aqueous NaCl. An adsorbed layer remained after complete exchange of the polyelectrolyte/surfactant solution for aqueous NaCl. In most cases, there was a codeposition of silicone oil droplets, if such droplets were present in the formulation before dilution. The overall features of the deposition were similar at hydrophobic and hydrophilic surfaces, but there were also notable differences. SDS molecules adsorbed selectively at the hydrophobized silica surface, but not at the hydrophilic silica, which influenced the coadsorption of the cationic polymers. The largest amount of deposited material after dilution was found for hydrophilic silica and for the least-hydrophobic cationic polymers. For the least-hydrophobic polyions, no significant codeposition of silicone oil was detected at hydrophobized silica after dilution if the initial SDS concentration was high.     

Transparent and conducting graphene-RNA-based nanocomposites

Ribonucleic acid (RNA) is proposed as a nonionic surfactant for the efficient exfoliation of graphite in thin flakes of few-layer graphene and the subsequent preparation of transparent and conducting thin films. Parameters such as the type of RNA used and the size of starting graphite flakes are demonstrated to be essential for obtaining RNA-graphene thin films of good quality. A model explaining the exfoliation of graphene by RNA in water is suggested. A number of post- and predeposition treatments (including thermal annealing, functionalization of the films, and the preoxidation of graphite) are critical to improve the performance of graphene-RNA nanocomposites as transparent conductors. The study establishes an ideal link between RNA and graphene, the fundamental building blocks for nanobiology and carbon-based nanotechnology.     

Disordered mesoporous silica low-k thin films prepared by vapor deposition into a triblock copolymer template film

Mesoporous silica films have been prepared by a vapor phase method using tetraethoxysilane (TEOS) in a batch reactor and in a continuous flow reactor. The TEOS molecules penetrated into a triblock copolymer films and then a triblock copolymer/silica composite structure was formed. A two dimensional grazing-incidence small angle X-ray scattering pattern and field emission scanning electron microscopy images of the films indicated that the films possess ordered and disordered regions. The tortuous pore channels in the wormhole-like disordered structure run parallel to the film surface. The mesostructured triblock copolymer/silica composite films were treated with a trimethylethoxysilane (TMES) vapor before and after calcination. The vapor infiltration treatments effectively improved mechanical strength and hydrothermal stability of the films. The dielectric constant of the TMES-treated mesoporous silica films was reduced into the 1.5–1.7 range.     

Constant chemical potential titration. Application to determination of nonionic surfactant concentrations

Titration is most often associated with the idea of a stoichiometric reaction. Generally, it is not considered possible to titrate a compound against a reagent unless the titration reaction is near total and if the result is not a product of well-defined stoichiometry. In this work, we illustrate that accurate titration is possible with compounds and reagents that interact to form an association of undefined stoichiometry. Our model is the potentiometric titration of nonionic surfactant with cationic surfactant using a cationic surfactant-selective electrode. The result of this reaction is mixed micelles, the composition of which depends on the concentrations of the two surfactants in solution.     

Preparation of Mesostructured Lamellar Zirconia

Mesostructured lamellar zirconia was synthesized in the hydrothermal systems using Cetyltrimethyl Ammonium Bromide (CTAB) as a template and zirconyl chloride as zirconium precursor. The as-prepared composites were characterized by X-ray diffraction (XRD), TG-DTA, and DR-UV techniques. The influences of hydrothermal aging time, total concentration of solution, different mole ratio of zirconyl chloride/surfactant, and post treatment on the structure of mesostructured lamellar zirconia were discussed in this article.     

Reflectance of surfactant-templated mesoporous silica thin films: Simulations versus experiments

In this study, cubic and hexagonal mesoporous amorphous silica thin films were synthesized using evaporation-induced self-assembly process followed by calcination leaving highly ordered spherical or cylindrical pores in a silica matrix. The films featured pores with diameter between 4 and 11 nm, lattice parameter from 7.8 to 24 nm, and porosity between 22% and 45%. All films were dehydrated prior to reflectance measurements except for one film which was fully hydrated. The present study compares the spectral reflectance measured experimentally between 400 and 900 nm with that computed numerically by solving three-dimensional Maxwell's equations in mesoporous silica thin films with the same morphology as those synthesized. The matrix was assumed to have the same optical properties as bulk fused silica. The pore optical properties were either those of air or liquid water whether the film was dehydrated or hydrated, respectively. Excellent agreement was found between experimental and numerical reflectance for both cubic and hexagonal mesoporous silica films. This study experimentally validates our simulation tool and offers the prospect of ab-initio design of nanocomposite materials with arbitrary optical properties without using effective medium approximation or mixing rules.     

采用结晶法制取改性硝铵的方法

文章介绍了用阳离子与非离子表面活性剂经复配后制取改性硝铵的方法,改性硝铵粒度分布情况及性状,改性后的硝铵爆炸性能有所改善.试验证明,混合表面活性剂的比例、搅拌时间、硝铵溶液浓度对改性硝铵的得率及性能均有影响.     

Fabrication of a magnetic helical mesostructured silica rod

We report a one-step synthesis of magnetic helical mesostructured silica (MHMS) by self-assembly of an achiral surfactant, magnetic nanocrystals with stearic acid ligands and silicate. This core-shell structured material consists of an Fe(3)O(4) superparamagnetic nanocrystal core and a highly ordered periodic helical mesoporous silica shell. We propose that the formation of the helical structure is induced by the interaction between the surfactant and dissociated stearic acid ligands. The MHMS obtained possesses superparamagnetism, uniform mesostructure, narrow pore size distribution, high surface area, and large pore volume. Furthermore, the drug release process is demonstrated using aspirin as a drug model and MHMS as a drug carrier in a sodium phosphate buffer solution.     

Generalized coating route to silica and titania films with orthogonally tilted cylindrical nanopore arrays

We describe a simple, inexpensive coating method to produce thin silica and titania films with surfactant templated, orthogonally tilted cylindrical nanopore arrays. These films can be deposited onto any substrate because orientation of the 2D hexagonally close packed (HCP) mesophases out of the plane of the film is directed by a chemically neutral sacrificial copolymer layer. Orientation of the HCP mesophases through the entire thickness of films cured in open air is achieved by limiting the coating thickness. This generalizes the coating method by making it possible to deposit oriented films on substrates of any curvature and size. We find a critical thickness between 70 and 100 nm, below which the triblock copolymer surfactant-templated HCP phase aligns completely out of the plane of glass and silicon wafer substrates. Above this thickness, the effect of the chemically neutral bottom layer does not propagate across the entire film, and alignment of the HCP mesophases parallel to the (nonpolar) air interface produces a mixed orientation.     

Preparation and characterization of low- and high-adherent transparent multi-walled carbon nanotube thin films

Thin films of multi-walled carbon nanotubes (MWNTs) were prepared by spin coating on borosilicate substrates. The precursor solution was a dispersion of MWNTs in water containing hexadecyl-trimethyl-ammonium-chloride (HDTAC), a cationic surfactant. In order to enhance the adhesion of the films to the substrate, different concentrations of an adhesion promoter were added to the precursor dispersion. Parameters such as the optimum concentration of MWNTs in the networks, temperature of heat treatment, transparency in the visible range, hardness and adherence of the films were investigated. The structural, optical, electrical and mechanical characterization of the thin films is demonstrated in this work.