Vibrational spectroscopic studies of vinyltriethoxysilane sol-gel and its coating

Infrared and Raman spectra of vinyltriethoxysilane (VTES), the VTES sol-gel, and the sol-gel coated aluminum have been collected. The assignments of the vibrational modes for the silane, the sol-gel, and the sol-gel films have been made based on the group frequencies and the spectral variation collected at different physical and chemical states of the sol-gel samples. Applying the sol-gels onto the metal grids allowed the drying and the high temperature treatment of the samples for the collection of infrared transmission spectra. From the variation of the sol-gel and the sol-gel coated aluminum IR spectra with temperature, it was noticed that the samples partially decomposed when the temperature was higher than 100 degrees C. Electrochemical experiments have demonstrated that the anticorrosion property of the coated aluminum has significantly increased. The water and the hexadecane contact angle measurements showed that the surface modified metal had a much higher hydrophobic property than the untreated metal.     

Vibrational spectra of metals treated with allyltrimethoxysilane sol-gel and self-assembled monolayer of allytrichlorosilane

A sol-gel has been prepared by using allyltrimethoxysilane (ATMS) as precursor, ethanol as homogenizer as well as solvent, and hydrochloric acid as catalyst. The sol-gel was employed for the coating treatment of aluminum. Self-assembled monolayer (SAM) with allyltrichlorosilane (ATCS) is another method used for the metal surface treatment in the present work. The treated metal surfaces were characterized with reflection adsorption infrared spectra (RAIR). Detailed interpretation and vibrational assignment have been given to the collected IR spectra of the sol-gel, xerogel and surface films of ATMS and the SAM of ATCS on aluminum as well as pure silanes. A series of investigation of the UV exposure and temperature effects has been carried out. Results from the investigation indicate that the UV radiation exposure or the high temperature thermal treatment will induce a chemical process on the organosilica coated surfaces.     

Vibrational spectroscopic studies of (3-mercaptopropyl)trimethoxylsilane sol-gel and its coating

Organosilane sol-gels have been prepared under different conditions from mercaptopropyltrimethoxysilane (MPTMS) and mercaptopropyltriethoxysilane (MPTES). These sol-gels were applied for the thin film coating on aluminum. Vibrational spectroscopy has been employed to trace and to study the proceeding of the sol-gel formation and the curing of the coated films on Al. Based on the group frequencies as well as their spectral behavior under different conditions, vibrational assignments have been made for most of the observed bands. Surface enhanced Raman scattering has revealed the chemical adsorption of MPTMS sol-gel on silver particles. Recorded reflection and absorption infrared (RAIR) spectra of coated tiles cured at different temperatures have indicated that surface reaction may occur at high temperature. The anticorrosion characters of the coated metals have been evaluated with the measured electrochemical data. Results from cyclic voltammographs have indicated that each layer of sol-gel coating would reduce the redox current across the electrode/electrolyte solution interface. Tafel plots have shown that the anodic current of the coated electrode decreases significantly and the corrosion potentials shift to the positive side.     

Spectroscopic studies of trimetoxypropylsilane and bis(trimethoxysilyl)ethane sol-gel coatings on aluminum and copper

Trimethoxypropylsilane (TMPS) and bis(trimethoxysilyl)ethane (BTMSE) were used as surface modifiers of metal vie the sol-gel process and dip coating. In addition to the single coating of Al, Cu and Sn, double treatments of Al were also conducted by combining coatings with these sol-gels in different sequences. Reflection and absorption infrared spectroscopy (RAIR) was employed to characterize and to trace the proceeding of the sol-gel process of the films. It was found that the silanol condensation occurs in the coating films on Al and the covalent linkage exists between the TMPS film and copper surface. From the assigned vibration modes, two conformers were identified in pure TMPS, TMPS sol-gel and coated film. A series of dip coating experiments with different concentrations of TMPS sol-gel was conducted, and the results from the collected RAIR spectra of the coated samples suggested that the coated Cu consistently has a better RAIR spectrum than that of the coated Al. The TMPS sol-gel appeared to have a better affinity to Cu than to Al. The temperature effect and the aging effect in the coating films were studied. X-ray photoelectronic spectroscopy (XPS) was employed to characterize the coated film, and the XPS data confirm the formation of the siloxane film from the silane coupling agents (SCA). Electrochemical impedance spectra (EIS) have been collected for bare Al and Cu, BTMSE sol-gel coated Al, and TMPS sol-gel coated Cu in 0.15M NaCl solution. The corresponding electronic circuit parameters have been determined to match the experimental EIS data.     

Spectroscopic studies of triethoxysilane sol-gel and coating process

Silica sol-gels have been prepared under different conditions using triethoxysilane (TES) as precursor. The prepared sol-gels have been used to coat aluminum for corrosion protection. Vibrational assignments have been made for most vibration bands of TES, TES sol-gel, TES sol-gel-coated aluminum and xerogel. It has been noticed that air moisture may have helped the hydrolysis of the thin coating films. Xerogels have been obtained from the sol-gel under different temperature conditions and the resulting samples have been characterized by using infrared and Raman spectroscopic methods. IR data indicate that the sol-gel process is incomplete under the ambient conditions although an aqueous condition can have slightly improved the process. Two nonequivalent silicon atoms have been identified from the collected (29)Si NMR spectra for the sol-gel, supporting the result derived from the IR data. The frequency of SiH bending vibration has been found to be more sensitive to the skeletal structure than that of the SiH stretching vibration. A higher temperature condition could favor the progression of hydrolysis and condensation. A temperature higher than 300 degrees C would cause sample decomposition without seriously damaging the silica network. From infrared intensity measurements and thermo-gravimetric analyses, the fractions of incomplete hydrolysis and condensation species have been estimated to be 4% and 3%, respectively. Electrochemical data have shown that the sol-gel coating significantly improves the corrosion protection properties of aluminum.     

Sol-gel coated polydimethylsiloxane/beta-cyclodextrin as novel stationary phase for stir bar sorptive extraction and its application to analysis of estrogens and bisphenol A

A sol-gel technique was used for the preparation of a stir bar coated with a composite composed of polydimethysiloxane and beta-cyclodextrin (PDMS/beta-CD). The sol-gel mechanism during coating procedure was discussed and successful binding of beta-CD to the sol-gel network was confirmed by the IR spectra. Scanning electron micrographs of the stir bars revealed a homogeneous surface with a film thickness of 30-150 microm attributing to different coating times. Good thermal stability and solvent-resistance of the stir bar were found thanks to chemical binding formed between the stationary phase and the glass substrate. The PDMS/beta-CD coated stir bar was proved to have better selectivity to polar compounds compared to the PDMS coated stir bar, and higher extraction capacity compared to the corresponding PDMS/beta-CD coated fiber. Methods for the determinations of estrogens in environmental water, bisphenol A in drinking water and in leachate of one-off dishware by the PDMS/beta-CD coated stir bar coupled with high-performance liquid chromatography (HPLC) were developed. The limits of detection were within the range of 0.04-0.11 microg l(-1) for estrogens using UV detection and 8 ngl(-1) for bisphenol A using fluorescence detection. Reproducibility with RSD less than 9.7% for extractions of real water samples at microg l(-1) or ngl(-1) level was obtained.     

Superhydrophilic/superhydrophobic surfaces fabricated by spark‐coating

In this study, the authors researched the preparations of superhydrophilic/superhydrophobic surfaces on commercial cup stock polyethylene coated papers by using sparked aluminum nanoparticles deposited on substrates through a sparking process. In this stage, the surface was porous and showed superhydrophilic properties. The samples were then annealed in air at various temperatures and some transformed to superhydrophobicity. It is well known that a suitable roughness in combination with low surface energy has been required to obtain superhydrophobic surfaces. Therefore, it is believed that during annealing process, when polyethylene is diffused from the substrate through the nanoparticle films and the superhydrophobic characteristics were created. The scanning electron microscope images showed that the film surfaces had a fluffy structure for both the as‐deposited and the annealed samples. However, the atomic force microscopy phase images showed completely different surface properties. Moreover, the X‐ray photoelectron spectroscopy spectra showed different surface chemical compositions. The experimental results revealed that the working temperature to produce superhydrophobic surfaces depended on the sparked film thickness. Furthermore, in order to prove the assumption explained above, glass and poly (methyl methacrylate) were also used as substrates.     

Thin films sensitive to pH changes prepared by sol-gel method

The light absorption change of phenolphthalein entrapped in a silica or titania matrix coated as a thin film onto a quartz optical fibre or on planar substrate by the sol-gel technique has been studied. The possibility to use this effect together with evanescent wave principle for the monitoring of pH changes has been tested. The film drying conditions necessary for the film to be sensitive to pH changes were determined experimentally. The stability and reversibility of the colour change was found to be better in the case of titanium matrix.     

牛血清白蛋白在超薄纳米二氧化钛膜表面的印迹与吸附

基于溶胶凝胶分子印迹方法,以溶胶二氧化钛TiO2为基质印迹了牛血清白蛋白分子。用1%的NaOH溶液可有效地除去纳米TiO2印迹膜中的模板分子。采用石英晶体微天平现场技术,研究了牛血清白蛋白在超薄纳米TiO2膜表面的吸附行为。研究表明,牛血清白蛋白在印迹膜和非印迹膜上的吸附量都随溶液浓度增加而增大,印迹膜具有吸附的特异性和可再生性,其吸附量是非印迹膜的3~5倍;在非印迹膜上的吸附符合Langmuir吸附模型,而在印迹膜上的吸附符合allosteric吸附模型;牛血清白蛋白在非印迹膜上的吸附量先随pH升高而增大,当pH为5左右时达到最大值,随后吸附量又随pH的增大而减小;而在印迹膜上其吸附量仅随pH增大而增大。     

Thermochromic Organoaminomodified Silica Composite Films Containing Phosphomolybdic Acid

A novel thermochromic sol-gel film has been prepared for the first time through entrapping phosphomolybdic acid into a kind of inorganic-organic matrix co-hydrolyzed from tetraethylorthosilicate and 3-aminopropyltriethoxysilane. The thus-obtained amorphous nanocomposite film was characterized by IR spectra, UV-vis absorption spectra, XRD, TG-DTA, and ESR. Results show that phosphomolybdate polyanions interact with R-NH⁺₃ cations strongly and disperse homogeneously in the sol-gel matrix. The sol-gel film exhibits thermochromic properties. Annealed from 120 to 180°C, the transparent film changes from pale-yellow to blue. A possible charge-transfer process has been suggested to explain the thermochromism.     

Enhanced removal of bilirubin on molecularly imprinted titania film

Titania film imprinted by bilirubin molecule at the surface of quartz crystal was prepared using molecular imprinting and surface sol-gel process. The molecularly imprinted titania film was characterized by FTIR spectra, and the interaction between bilirubin and imprinted film was investigated using quartz crystal microbalance (QCM) technique. Compared with pure titania film, the molecularly imprinted titania film exhibits a much higher adsorption capacity for the target molecule, and the adsorption kinetic parameter estimated from the in situ frequency measurement is about 1.6×10(8) M(-1), which is ten times higher than that obtained on pure titania film. The photocatalytic measurements indicate that the bilirubin adsorbed on molecularly imprinted titania film can be completely removed under UV illumination. Moreover, our study indicates that the molecularly imprinted titania film possesses a better stability and reusability.     

脱氟化氢聚偏氟乙烯膜的制备, 表征和导电性能的研究

聚偏氟乙烯(PVDF)膜与一些有机弱碱作用脱氟化氢(HF)生成表面为一氟乙炔(PFA)的膜。红外、紫外可见光谱分析表明脱HF的PVDF膜的共轭链结构比较规整。X光电子能谱、反应深度和接触度的分析表明, PVDF脱HF反应主要发生在膜表面。脱HF的PVDF膜(PFA)经各种掺杂剂掺杂后电导率上升5~6个数量级, 最高可达10^-^4s/cm, 且在掺杂过程中出现出的性质不同于聚乙炔。     

Surface plasmon-coupled polarized emission of N-acetyl-l-tryptophanamide

We report an observation of ultraviolet (UV) surface plasmon-coupled emission (SPCE) of N-acetyl-l-tryptophanamide (NATA). The sample was spin coated from poly(vinyl alcohol) (PVA) solution on 20 nm aluminum film deposited on a quartz substrate. The directional UV SPCE occurs within a well-defined narrow angle at 52 degrees from the normal to the coupling hemicylinder quartz prism. The NATA directional emission is highly p polarized as expected for surface plasmon-coupled radiation. The 10 nm protective SiO2 layer deposited on top of the aluminum film significantly neutralized the fluorophore quenching by the metal surface. SPCE of NATA demonstrates a remarkable intrinsic dispersive property-the maximum of the emission spectrum depends on the observation angle. The efficient spectral resolution of SPCE can be used in the construction of miniaturized spectrofluorometers. The observation of SPCE of tryptophan opens a new possibility for the study of many unlabeled proteins with the technique complementary to surface plasmon resonance analysis.     

Synthesis of TiO2 thin film by a modified sol-gel method and properties of the prepared films for photocatalyst

PTA (peroxo titanic acid) gel was prepared by a modified sol-gel method from peroxo titanic acid using TiCl₄/ethanol/water solution as the starting material at room temperature. Physicochemical properties of heat-treated gel were characterized by IR, XRD, TG-DTA and SEM. Optimal preparing conditions were chosen to prepare anatase film for the photocatalytic degradation of methyl orange. The dip-coating technique was used to synthesis the supported anatase film on quartz glass. Photocatalytic efficiency for the degradation of methyl orange under UV irradiation was also examined. It was found that the degradation efficiency of the anatase film synthesized in this paper is higher than commercial titania P25.     

Deposition of Oral Bacteria and Polystyrene Particles to Quartz and Dental Enamel in a Parallel Plate and Stagnation Point Flow Chamber

The aim of this paper is to determine to what extent (i) deposition of oral bacteria and polystyrene particles, (ii) onto quartz and dental enamel with and without a salivary conditioning film, (iii) in a parallel plate (PP) and stagnation point (SP) flow chamber and at common Peclet numbers are comparable. All three bacterial strains showed different adhesion behaviors, and even Streptococcus mitis BMS, possessing a similar cell surface hydrophobicity as polystyrene particles, did not mimic polystyrene particles in its adhesion behavior, possibly as a result of the more negative ζ potentials of the polystyrene particles. The stationary endpoint adhesion of all strains, including polystyrene particles, was lower in the presence of a salivary conditioning film, while also desorption probabilities under flow were higher in the presence of a conditioning film than in its absence. Deposition onto quartz and enamel surfaces was different, but without a consistent trend valid for all strains and polystyrene particles. It is concluded that differences in experimental results exist, and the process of bacterial deposition to enamel surfaces cannot be modeled by using polystyrene particles and quartz collector surfaces.     

Electrochemical Preparation of Poly(Malachite Green) Film Modified Nafion‐Coated Glassy Carbon Electrode and Its Electrocatalytic Behavior Towards NADH,Dopamine and Ascorbic Acid

Poly(malachite green) film modified Nafion‐coated glassy carbon electrodes have been prepared by potentiodynamic cycling in malachite green solution. The pH of polymerisation solution has only minor effect on film formation. Electrochemical quartz crystal microbalance (EQCM) was used to monitor the growth of the poly(malachite green) film. Cyclic voltammogram of the poly(malachite green) film shows a redox couple with well‐defined peaks. The redox response of the modified electrode was found to be depending on the pH of the contacting solution. The peak potentials were shifted to a less positive region with increasing pH and the dependence of the peak potential was found to be 56 mV per pH unit. The electrocatalytic behavior of poly(malachite green) film modified Nafion‐coated glassy carbon electrodes was tested towards oxidation of NADH, dopamine, and ascorbic acid. The oxidation of dopamine and ascorbic acid occurred at less positive potential on poly(malachite green) film compared to bare glassy carbon electrode. In the case of NADH, the overpotential was reduced substantially on modified electrode. Finally, the feasibility of utilizing poly(malachite green) film electrode in analytical estimation of ascorbic acid was demonstrated in flow injection analysis.     

电化学阻抗谱法研究环氧膜的渗水机理

本工作测量了覆盖环氧膜的铝电极在NaCl溶液中的电化学阻抗谱, 并求得了该膜的膜电阻、膜电容和环氧膜与底金属间的腐蚀电阻及双电层电容。由膜电容求得该膜的介电常数为5.2。此种膜未浸入NaCl溶液前的介电常数为4.9。将上述数据与未覆盖环氧膜的铝电极的电化学阻抗数据比较, 可认为溶液是经上述膜中的化学通道而渗入膜内的。     

Adsorption of cationic starch on cellulose studied by QCM-D

The adsorption of cationic starch (CS) from aqueous electrolyte solutions onto model cellulose film has been investigated by the quartz crystal microbalance with dissipation monitoring (QCM-D) and X-ray photoelectron spectroscopy (XPS). The influence of the electrolyte composition and charge density of CS was examined. The adsorption of CS onto cellulose followed the general trends expected for polyelectrolyte adsorption on oppositely charged surfaces, with some exceptions. Thus, as result of the very low surface charge density of the cellulose surface, highly charged CS did not adsorb in a flat conformation even at low ionic strength. The porosity of the film, however, enabled the penetration of coiled CS molecules into the film at high electrolyte concentrations. Differences between the adsorption behavior of CS on cellulose and earlier observations of the adsorption of the same starches on silica could be explained by the different morphologies and acidities of the hydroxyl groups on the two surfaces.     

Sol-Gel Protection of Front Surface Silver and Aluminum Mirrors

SiO₂ sol-gel dense and thin coatings have been applied by dipping to protect front surface silver and aluminum mirrors, prepared by different deposition techniques onto glass and metallic substrates. Integrated solar reflectances over 0.95 for coated silver and 0.85 for coated aluminum are obtained, the mechanical stability depending on the metal (Ag, Al), on the deposition method and on the substrate. These front surface mirrors present high and long thermal stability up to 300°C, good outdoor resistance, lower weight and the production method is simple and cheap enough to be applied in solar energy applications.     

电化学阻抗法研究环氧膜的吸水性能

电化学阻抗法研究环氧膜的吸水性能罗小雯，陈月辉，李善君，周伟舫（复旦大学高分子科学系，化学系，上海，２００４３３）关键词电化学阻抗谱，环氧膜，交联密度，吸水性能水在环氧树脂膜中有较强的吸收和扩散能力，例如ＸＤ７３４２／ＴＭＡＢ于１９５℃固化２４ｈ，在...