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.     

3-(Triethoxysilyl)propionitrile sol-gel coating

3-(Triethoxysilyl)propionitrile (TESPN) sol-gel has been prepared under different conditions. It was employed for coating the surfaces of quartz and aluminum. Infrared (IR) and Raman spectra of TESPN and TESPN sol-gels have been recorded in the study of the sol-gel process. Transmission and reflection absorption IR (RAIR) spectra of TESPN sol-gel coated quartz and aluminum have also been collected for better understanding the film formation on the substrate surfaces. Spectra collected at different temperatures indicated that the silane film on quartz decomposes at 700 degrees C. Results from thermal gravimetric analysis (TGA) supported this result. Based on the group frequencies and the spectral behavior in different states, some vibrational modes were assigned to the observed bands. The anticorrosion behavior of the sol-gel coated aluminum in comparison with the uncoated metal was evaluated by measuring the potentiodynamic polarization and electrochemical impedance spectra (EIS).     

Studies of thiol additions of silane coupling agents by vibrational spectroscopy

Raman and infrared spectroscopies have been used to determine the addition reaction of mercaptopropyltrimethoxysilane (MPTMS) to allyltrimethoxysilane (ATMS) and 7-octenyltrichlorosilane based on the vibrational intensity variation of thiol and vinyl groups in the reaction mixtures. Due to the distinct and moderate intensity of Raman bands observed in the present experiment, the identification with Raman spectroscopic method is more sensitive than that with FTIR spectroscopy. In the presence of UV radiation, thiol addition reaction has been observed in the direct mixing samples of silanes. Hybrid sol-gels prepared with the use of MPTMS and ATMS as precursors in both acidic and basic conditions have revealed the progression of thiol addition under the UV radiation exposure. UV radiation is similarly effective to induce the thiol addition in the sol-gel coated aluminum tiles. Without UV radiation, the use of free radical initiator in the sol-gel samples might also help to induce the addition reaction.     

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.     

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.     

Protective Properties of a Sol-Gel Coating on Zinc Coated Steel

Galvanised and galvannealed steels are widely used due to their good corrosion resistance in aqueous solutions. However, when additional protection is required, organic coatings, corrosion inhibitors or conversion coatings are used to improve their corrosion protection. In this work, sol-gel coating was used to improve the corrosion behaviour of these two materials. This paper analyses the final protective properties of a sol-gel coating prepared by basic catalysis and its dependence on the sintering temperature and time of treatment. The influence of the sintering conditions on the galvanised and galvannealed substrates is a decisive factor for the coating quality and for the barrier affect against the aggressive media. While heat treatment time is the controlling factor for the galvannealed steels, the temperature is determining in the case of the galvanised. Corrosion mechanisms for sol-gel galvanised steels did not changed with respect to the uncoated steel. However for galvannealed steel, after coating the mechanism is not purely cathodic.     

Vibrational spectra of phenyltriethoxysilane, phenyltrimethoxysilane and their sol-gels

Raman and infrared spectra of phenyltriethoxysilane and phenyltrimethoxysilane have been recorded. These silane coupling agents (SCAs) have been used as precursors to prepare sol-gels using acid or base as catalyst under different solution conditions. From the vibrational spectroscopic identification, it was found that the major sol-gel products obtained from different catalysts and different solvents were essentially the same. Vibrational assignments for the SCAs, sol-gel and xerogel have been made based on the group frequencies, the spectral variation collected at different physical and chemical states and the previous spectroscopic studies of similar molecules. The compositions of xerogels after thermal treatments at different temperatures have been analyzed and identified by using infrared spectroscopic method along with thermal gravimetric analysis. Results from the experimental treatments for the xerogels indicated that the xerogel baking at 118 degrees C served to evaporate the sample moisture, the curing at 225 degrees C helped to complete the condensation reaction, and the treatment at 600 degrees C caused the decomposition of the organic group but the siloxane net-work remained essentially unchanged.     

Effect of Solution Chemistry on Preparation of Boehmite by Hydrothermal Assisted Sol-Gel Processing of Aluminum Alkoxides

Various aluminum alkoxide precursors have been used for the preparation of boehmite by hydrothermal assisted sol-gel processing. The coordination status of aluminum in solution for all precursors employed for the preparation of boehmite phase was determined by ²⁷Al NMR and correlation between coordination status of aluminum atoms of precursors and development of boehmite phase has been investigated. Hydrothermal assisted hydrolysis of aluminum alkoxides where the aluminum atoms are four or five coordinated in solution resulted in the formation of boehmite. In contrast, hydrothermal hydrolysis of aluminum alkoxides where the aluminum atoms are six coordinated resulted in the formation of amorphous gel. Development of boehmite phase by hydrothermal hydrolysis of aluminum alkoxides at various temperatures was pursued by X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy.     

Synthesis, infrared stealth and corrosion resistance of organically modified silicate-polyaniline/carbon black hybrid coatings

Hybrid coatings based on organically modified silicate-polyaniline/carbon black (Ormosil-PANI/CB) were synthesized through a sol-gel technique with different carbon black (10-30 wt%) and PANI/CB (10-30 wt%) contents. These hybrid films were deposited via spin coating onto an aluminum alloy in order to improve the corrosion protection and to act as infrared stealth coatings. The effects induced by the PANI/CB composites on the chain dynamic, thermal properties, infrared stealth, and anticorrosion performances of the coated samples were investigated. The rotating-frame spin-lattice relaxation times and scale of the spin-diffusion path length indicated that the configuration of the hybrid films was highly cross-linked and dense. Thermal properties of these Ormosil-PANI/CB hybrids have been improved over the pure Ormosil analyzed by thermal gravimetric analysis (TGA). The thermal extinction of the hybrid coatings increased with the increase in the carbon black and PANI/CB content. Potentio-dynamic and salt-spray analysis revealed that the hybrid films provided an exceptional barrier and corrosion protection in comparison with untreated aluminum alloy substrates.     

Optical properties of a polyethylene dispersion with a luminescent silica prepared by surface grafting of a perylene derivative

A micrometric silica modified with perylene derivative (SiO₂–TES) has been prepared by hydrolysis–condensation reactions between silica and N,N’-bis-(3-triethoxysilylpropyl)-perylene-tetracarboxyldiimide (P-TES) and utilized as filler in LLDPE films together with a compatibilizer. Spectroscopic analyses on SiO₂–TES confirmed the grafting of P-TES on silica, while its amount was determined by thermogravimetric analysis. Solid state NMR provided information about the structure of silicon atoms involved in the condensation of SiO₂ and P-TES that resulted mainly in silicon atoms grafted with bi-dentate anchorages.UV–Vis and fluorescence analyses carried out on P-TES showed the ability of the dye to generate J-type aggregates in apolar solvents. The same analyses on SiO₂–TES revealed the presence of both isolated and aggregated dye molecules grafted on silica surface, while on polymeric dispersions of SiO₂–TES, they have shown only the presence of P-TES aggregates grafted to silica.Thanks to the direct correlation between optical properties (obtained both by UV–Vis and by fluorescence analyses) and the chemical environment of composites, the luminescent silica SiO₂–TES could be used to estimate the filler dispersion extent in different microcomposite polymer materials.     

Zn-Al-[V10O28]6-双层氢氧化物掺杂对LY12铝合金表面溶胶-凝胶涂层性能的影响

采用共沉淀法制备Zn-Al-[V₁₀O₂₈]^6-双层氢氧化物(以下简称LDH-V), 研究不同添加浓度(0.0、0.25×10^-3、0.75×10^-3、1.5×10^-3、3.0×10^-3 mol·L^-1)的LDH-V对LY12 铝合金溶胶-凝胶涂层形貌、耐蚀性的影响. 采用扫描电子显微镜(SEM)和傅里叶变换红外(FTIR)光谱研究LDH-V对涂层形貌和结构的影响. 运用中性盐雾实验对涂层进行耐蚀性评估. 利用电化学方法对涂层在0.05 mol·L^-1的NaCl 溶液中的腐蚀行为进行研究. 探讨加入LDH-V后溶胶-凝胶涂层的耐蚀机理. 结果表明, 一定量LDH-V的加入不仅可以提高溶胶-凝胶涂层的耐蚀性能, 还可对涂层被破坏区域进行自修复, 起到延缓铝合金基体腐蚀的作用. 然而, 当LDH-V的添加溶度超过一定值时, 会破坏涂层的完整性并降低涂层的腐蚀防护性能. 实验结果表明LDH-V最佳的添加浓度为1.5×10^-3mol·L^-1.     

Catalytic Effects of Aluminum Butoxyethoxide in Sol-Gel Hybrid Hard Coatings

Hybrid inorganic-organic hard coatings on PMMA substrate were obtained by sol-gel reaction of 3-glycidoxypropyltrimethoxysilane(GPTS), tetramethyl orthosilicate(TMOS) and aluminum butoxyethoxide (Al(OEtOBu)₃). The catalytic effect of aluminum butoxyethoxide on inorganic condensation and epoxide polymerization has been studied by ¹³C, ²⁹Si nuclear magnetic resonance spectroscopy and by Fourier transformed infrared spectroscopy. Hardness of hybrid inorganic-organic materials were measured by nanoindentor and mainly influenced by the extent of epoxide polymerization and inorganic condensation of their coating catalyzed by aluminum butoxyethoxide.     

Sol-Gel Coatings on Metals

Sol-gel derived films can be deposited on metals to improve their resistance to oxidation and corrosion or to modify their surface properties. However, practical applications are limited by problems intrinsic to sol-gel processing or specific of coating/metal systems. Coatings aimed to improve oxidation and wet corrosion resistance have been the most studied. The results published in the literature show that sol-gel coatings may offer good protection against oxidation. More difficult is to achieve a protection against wet corrosion. An important aspect of the application of the sol-gel method for coating metallic objects is also the deposition technique.     

Electrochemical behaviour of SiO2 sol-gel coatings on stainless steel

SiO₂ coatings onto stainless steel substrates have been prepared by sol-gel in order to study the performance and mechanism of attack in different corrosive solutions. The electrochemical behaviour of the samples has been evaluated by Electrochemical Impedance Spectroscopy using NaCl and HCl as electrolytes. Comparative tests have been performed on samples with one and two silica layers as well as on uncoated ones. SiO₂ coatings produce no important protection of stainless steels subjected to electrochemical corrosion. This behaviour may be explained by micropores and microcracks produced during the coating sintering.     

A novel sol-gel calix[4]arene-modified capillary column for open-tubular capillary electrochromatography

A novel open-tubular CEC (OT-CEC) column was prepared by immobilized 5,11,17,23-tetra-tert-butyl-25,27-diethoxy-26,28-dihydroxy-calix[4]arene (Calix[4]) on fused-silica capillary column with sol-gel technology. Calix[4] was initially reacted with gamma-glycidoxypropyltrimethoxysilane (KH-560) to form a new sol-gel precursor (calix[4]-KH-560), and then mixed with another precursor, namely tetraethoxysilane (TEOS). After hydrolysis and condensation, a sol-gel matrix was obtained, in which calix[4] was incorporated. Successful calix[4]-modified sol-gel coating was suggested by infrared (IR) spectra and greatly decreased EOF. In comparison with OT columns prepared by the sol-gel method with TEOS and KH-560 only, the calix[4]-modified sol-gel column showed greatly improved separation of isomeric toluidines, nitrophenols, picolines and neurotransmitters with structural similarity. Migration time and theoretical plate number reproducibility were satisfactory with RSDs less than 1 and 6% each for within column runs and not more than 3 and 7% each for column-to-column measurements, using toluidine and nitrophenol isomers as test solutes on this column. High separation efficiencies (96,000-300,000 plates/m) for basic toluidine isomers were obtained. This column was also successfully employed to combine extraction procedure for the determination of dopamine (DA) and norepinephrine (NE) in Portulaca oleracea L. The recoveries of DA and NE were 93.3 and 94.2%, respectively.     

Preparation of unsupported alumina membrane by sol-gel techniques

Unsupported alumina membranes were prepared by sol-gel technique using aluminum isoproxide. The influence of the hydrolysis conditions, the type and concentration of peptizant acid on the boehmite sols has been studied. The suitable hydrolysis temperature for the aluminum isoproxide was above 50°C. Crack-free unsupported alumina membranes were obtained by rapid gelation processing of sols. The boehmite gel membrane and γ-Al₂O₃ membrane formed exhibited (020) and (440) preferred orientation.     

Synthetic control of cage/network ratio of poly(methylsilsesquioxane)s for storage stability,hardness, and weather resistance of coating films

Poly(methylsilsesquioxane) (PMSQ) was synthesized using a two‐step process consisting of hydrolysis of methyl trimethoxysilane (MTMS) with aluminum chelate catalyst and successive condensation reactions conducted at elevated temperatures. Results of nuclear magnetic resonance and Fourier transform infrared measurements show that all terminal functional groups were Si? OH in PMSQ. Results show further that PMSQ has both a cage structure and a network structure, and a cage/network ratio is represented by a height ratio of ?64.5/?66.6 ppm. PMSQ of different molecular weight but the same Si? OH concentration is obtainable by varying the condensation reaction conditions such as the concentration, temperature, amount of aluminum chelate catalyst, and the solvent solubility parameter. A difference of the cage/network ratio occurs. A different cage/network ratio is dependent on the different reactivities of the intramolecular and intermolecular reactions. The relations of molecular structure of the obtained PMSQ molecular structure were characterized along with functions of storage stability, film hardness, and weather resistance. PMSQ designed with a larger cage/network ratio is necessary to obtain PMSQ with good storage stability and a coating film having good weather resistance. PMSQ designed with a smaller cage/network ratio should be prepared to obtain a coating film with high hardness. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

GdAlO_3:Er~(3+),Yb~(3+)荧光粉的制备与上转换发光性能

采用共沉淀、溶胶-凝胶和固相反应法制备了GdAlO3:Er3+,Yb3+荧光粉.借助X射线衍射、扫描电子显微镜、傅里叶变换红外光谱、N2-吸附、吸收光谱和荧光光谱等手段研究了不同方法制备的GdAlO3:Er3+,Yb3+荧光粉结构、形貌、表面基团和光吸收及上转换发光性能.结果表明:用共沉淀法比固相反应法和溶胶-凝胶法可以在更温和的条件下制得纯相GdAlO3:Er3+,Yb3+荧光粉,用共沉淀法和溶胶-凝胶法制备的GdAlO3:Er3+,Yb3+荧光粉颗粒都在纳米尺寸,溶胶-凝胶法制得的样品存在相对严重的颗粒团聚现象,而用固相反应法制备的荧光粉为微米级颗粒.GdAlO3:Er3+,Yb3+荧光粉在980 nm激发的上转换发射光谱包含波长为524和546 nm的绿光与659 nm的红光,且三种方法制备的样品绿光发射强度都显著高于红光.不同方法制备的荧光粉上转换发光强度和红光/绿光强度比相差较大,共沉淀法制备的样品上转换发光强度要显著高于固相法以及溶胶-凝胶法制备的样品,而溶胶-凝胶法制备的样品发光中红光/绿光相对强度比最高.红外光谱显示,不同方法制备的GdAlO3:Er3+,Yb3+荧光粉表面OH-、CO32-及CO2官能团含量不同,溶胶-凝胶法制备的样品要明显高些.基于红外光谱、不同Er3+和Yb3+离子掺杂浓度及不同激光功率上转换发光的结果,对Er3+和Yb3+之间的能量传递过程及不同方法制备荧光粉的上转换发光性能进行了讨论.     

Sol-Gel Deposition of ZrO2 Films in Air and in Oxygen-Free Atmospheres for Chemical Protection of 304 Stainless Steel: A Comparative Corrosion Study

ZrO₂ coatings for corrosion protection were deposited on 304 stainless steel by sol-gel method using zirconium propoxide as precursor and densified in air and in oxygen-free (argon or nitrogen) atmospheres. XRD and IR data of the films were practically independent of the atmosphere used in the densification step showing that the ceramic oxide is properly formed from the precursor. The corrosion behavior of the stainless steel substrate was studied by potentiodynamic polarization curves in the absence and the presence of ZrO₂ coatings prepared in air, argon or nitrogen. The coatings extended the lifetime of the material by a factor of almost eight in a very aggressive environment, independently of the preparation procedure. The possibility of depositing pure or mixed oxide films by sol-gel methods in the absence of additional oxygen will allow the preparation of specific coatings onto oxygen-reactive substrates.