Elastic modulus profiles in the cross sections of drying alkyd coating films: modelling and experiments

The temporal development of the modulus of elasticity and its profile were studied in water-borne alkyd coatings during the drying process of the coating films. Values of the Young’s moduli of elasticity of free coating films were measured using tensile tests. Since the elastic modulus is related to cross-link density, the values of the moduli give information on the advancement of the drying process. A mathematical model was developed to predict the degree of effective cross-linking and the mechanical behaviour of the drying coating films with different thicknesses. This model is based on trends observed by confocal Raman microspectroscopy, which exhibit the profile of the consumption of double bonds and thus can be used to monitor the development of cross-link density as a function of depth from the film surface. The average values of the Young’s measured moduli were successfully described by the numerical model as a function of drying time.     

Microporous silica membranes deposited on porous supports by filtration

Water based particulate silica sols have been coated onto Anodisc® filters by filtration. The membranes prepared by this technique are more uniform than those formed by slip-casting. The average diameter of the silica particles used in these studies is 6 nm. Unsupported silica membranes formed from these sols have a microporous structure. The adhesion between silica and the alumina support is influenced by the sol pH. Coating thickness can be controlled by the concentration and volume of the sol filtered. Polyvinyl alcohol (PVA) was used to improve adhesion and to prevent cracking during drying. When the PVA/SiO₂ ratio by weight is less than 20%, the membranes retain their microporosity after firing. The membranes prepared by this filtration method have their pore size in Knudsen diffusion range.     

Formation of Al2O3–BaTiO3 nanocomposite oxide films on etched aluminum foil by sol–gel coating and anodizing

Barium titanate BaTiO₃ (BT) sol was dip-coated on the etched aluminum foils by a sol–gel process. After annealed at 600 °C in air, the foils were anodized in ammonium adipate solution. The voltage–time variations during anodizing were monitored. The structure, composition, and electric properties of the anodic foils were investigated. The obtained foils were fabricated into aluminum electrolytic capacitors and the load and shelf life test were measured. It was found that the slope of the voltage–time curve of aluminum foil covered with BT films became steeper. A triple layer of Al/Al₂O₃/BT was formed after anodizing Al/BT foil. The specific capacitance and the product of specific capacitance and withstanding voltage of anodic foil with a BT coating were about 46.36% and 38.90% larger than that without a BT coating. After the load life and shelf life of 2500 h at 85 °C, two kinds of capacitors have similar behaviores and meet with Nichicon standard of Japan. From the results, BaTiO₃ is promising to be used as the dielectric of aluminum electrolytic capacitor to increase the specific capacitance.     

Wettability and photodegradation activity of sol–gel dip-coated zinc oxide films

The hydrophilic characteristics of zinc oxide combined with the electronic properties of this width band gap semi-conductor were used to produce transparent, anti fog and photocatalytic porous films by using a simple sol?Cgel dip-coating process. The observed values of contact angles (near to 10°) and calculated spreading coefficients (close to zero) indicate that sol?Cgel dip-coated ZnO porous films show excellent wettability. The photocatalytic behavior of these films measured from methylene blue degradation is dependent on the film thickness in agreement with wettability results; as the film thickness increases from 0.1?±?0.05 to 0.5?±?0.05 the photocatalytic reaction rate constant increases from 0.9?×?10^?3 to 5.5?×?10^?3 min^?1.     

Preparation of Alumina Aerogel Films by Low Temperature CO2 Supercritical Drying Process

Alumina aerogel thin films were formed by a new synthesis route. Sols were prepared by the Yoldas process. Gels were formed by sol evaporation in a few hours. Films were prepared by dip coating glass or alumina substrates into both the sols and the gels. Aerogel films with special morphology were produced for the first time by exchanging the film solvent with acetone after the dip coating, followed by supercritical drying. The morphology of the films, studied by SEM and TEM, consists of fiber-like network of round chains (≈0.1 μm thick), and pores (0.1–0.5 μm in diameter). It is shown that the fibers contain a homogeneous arrangement of sol particles, 2–4 nm in size. Formation of this microstructure can be attributed to phase separation in the alumina-water-acetone system in a 2D film geometry. A conceptual model for the film development is proposed.     

Luminescence quenching of tris(2,2'-bipyridine)ruthenium(II) by 2,6-dimethylphenol and 4-bromo-2,6-dimethylphenol in sol-gel-processed silicate thin films

The luminescence properties of tris(1,2-bipyridine)ruthenium(II) (Ru(bpy)(3)(2+)), included in different organically modified silicate gel matrixes were investigated. Spin and dip-coated thin films were prepared from methyltrimethoxysilane (MTMOS) and methyltriethoxysilane (MTEOS). A blue shift in the emission spectrum of the MLCT excited state of Ru(bpy)(3)(2+) with respect to the aqueous solution was observed in all the films, practically independent of the reaction pH used to prepare the "sol," silane-derived precursor, and procedure used (dip-coating or spin-coating) to obtain the film. A bimodal distribution of probe sites in the films was obtained from modeling of the emission decays by a double exponential and from application of the exponential series method. The parameters of the decay components depended principally on the thermal treatment used in the processing of the films. The lifetimes decreased with the increase in the drying temperature of the films; at the same time, the emission spectra showed a red shift and the luminescence efficiency decreased. A luminescence quenching of the ruthenium complex in the films by 4-bromo-2,6-dimethylphenol and 2,6-dimethylphenol in aerated aqueous solution at pH 12 in contact with the film was also observed. The quenching plots obtained from luminescence intensities or luminescence intensity decay measurements showed a downward curvature. These plots could be fitted satisfactorily by a sum of two Stern-Volmer terms with quenching constants K(SV1) and K(SV2) associated with two different binding sites of the ruthenium complex. This result is indicative of the matrix microheterogeneity in the films and is fully consistent with the biexponential nature of the luminescence intensity decay profiles. The Stern-Volmer parameter values for both sites in the films suggest that only a low percentage of the probe is accessible to the quencher and its respective constant K(SV1) is lower than in water.     

Lead Zirconate Titanate Stable Stock Solution: Characterization and Applications

Lead zirconate titanate (PZT) thin films were prepared by the sol-gel process using acetic acid and 1,2-propanediol as solvents. Acetone was used as final solvent and in this way a stable stock sol (for more than 12 months) was obtained. The PZT sols prepared were reproducible and suitable for the preparation of PZT thin films. To study the sol structure evolution gas chromatography mass spectrum (GC-MS) and Fourier-transform-infrared (FT-IR) spectra were recorded and analyzed on each step of the synthesis. The rheological behavior and the stability of the stock sol were checked using a rheometer. It is observed that the addition of acetone leads to a very stable stock sol. The preliminary investigation of the electric properties of the obtained PZT thin films showed that the crystallized films deposited from a fresh prepared sol and a 12 months aged sol exhibit similar ferroelectric properties and comparable to those reported in the literature.     

医用多孔NiTi合金表面溶胶-凝胶法制备TiO2涂层

采用溶胶-凝胶法结合浸渍提拉工艺在多孔NiTi合金表面制备出了结构均一的锐钛矿型TiO2涂层,并在溶胶中添加聚乙二醇(PEG)作为造孔剂,进而在多孔NiTi合金表面制备出内层致密、外层多孔的TiO2复合涂层。SEM分析结果表明,TiO2涂层均匀地覆盖了多孔NiTi合金基体的外表面以及孔的内表面。Hanks溶液中的阳极极化曲线结果表明,与未处理的多孔NiTi合金相比,具有致密TiO2涂层的多孔NiTi合金其耐腐蚀性能有了显著提高。而多孔TiO2复合涂层进一步增大了多孔NiTi合金的实际表面积,提高了材料表面的生物活性。     

Sol-gel synthesis and characterization of yttria stabilized zirconia membranes

Mesoporous yttria stabilized zirconia (YSZ) membranes can be used as supports for ultrathin dense ceramic or metallic membranes, and for ultrafiltration (UF) applications in harsh environments. This paper reports synthesis and characterization of sol-gel derived UF YSZ membranes. 0.25 M zirconia sol was prepared by hydrolysis and condensation of zirconium n-propoxide. A solution-sol mixing method was used to dope 8 mol% yttria in zirconia. Supported YSZ membranes were prepared by dip-coating the yttrium doped zirconia sol on the porous α-alumina substrate, followed by drying and calcining under controlled conditions. The membranes prepared in this study are of cubic fluorite phase. Helium permeation experiments show that the supported membranes are pin-hole (or crack) free. The 5 time dip-coated membrane determined by SEM micrograph is about 3.5 μm in thickness, with an average pore diameter of 3 nm.     

Temperature programmed desorption analysis of sol-gel-derived titania films

Sol-gel-derived titania films were analyzed by temperature programmed desorption (TPD) and X-ray diffraction (XRD) techniques. The relationship between the TPD curves measured for two types of titania gel films and their crystal structures was investigated. On the basis of the analyses, a preparation process for a titania sol solution containing anatase nanocrystals was designed and developed. Using this process, a colloidal anatase titania sol solution was prepared by heating aqueous titanium hydroxide containing HCl at 60°C for 2 h. The nanocrystal structure of the titania films obtained by coating the sol on glass substrates was confirmed by TPD and XRD measurements.     

Formation and drying of colloidal crystals using nanosized silica particles

Much interest has been generated in the fabrication of colloidal crystals from suspensions because of the promise of photonic band gap applications. However, since the case of small, nonsedimenting colloidal particles indeed remains rather rarely treated, spherical silica particles with diameters varying from 75 down to 20 nm have been used in the present work to fabricate colloidal crystals by drying the suspending liquid. Typical events that take place during the drying process of a particulate film, such as cracking, compaction and penetration of air into a porous network, have been evaluated using existing theories, and the maximum stress in the drying film could be approximated. Investigation on the dry film structure by scanning electron microscopy showed the arrangement of particles in a close-packed system. To interpret the formation of such crystals, the amplitudes of the interparticle and capillary forces have been estimated from existing models. The repulsive interparticle forces allow the particles to remain stable and thus rearrange up to fairly high particle concentration. These modeling results showed the dominance of the capillary contribution at the end of the drying process. Nitrogen adsorption/desorption measurements gave very coherent results regarding both pore volume and pore size of the dry particulate films when compared to the expected ordered packing arrangements.     

Synthesis and structure features of composite silicate and hybrid TEOS-derived thin films doped by inorganic and organic additives

The results of long-term researches of thin films prepared from tetraethoxysilane-derived sols containing inorganic and organic additives are systematized and analyzed. These additives give to films certain physicochemical properties for their application in electronic techniques, optics, power engineering, in biological technologies etc. The influence both inorganic (salts, acids) and organic (polyols, polyionenes, epoxy resin) additives on rheological properties and aggregate stability of sols as well as films surface morphology is minutely considered. The explanations of phenomena during film formation, including spin-coating process, are given. Essential influence of temperature and humidity on films surface morphology is shown. Influence of heat treatment modes on structure and composition of films is analyzed. Recommendations about optimization of thin films sol–gel processing are offered.     

Laser reflectometry to investigate adsorption–desorption of poly(styrene sulfonate) onto polyamide 6.6

The adsorption of poly(styrene sulfonate) (PSS) on polyamide 6-6 was investigated using fixed angle laser reflectometry. The appropriate polyamide film thickness for an accurate analysis was first determined theoretically. Polyamide films were further prepared at controlled thickness using dip-coating processes and characterized. The adsorption of PSS was measured at pH 3 on dip-coated films as a function of time and polymer concentration. The adsorption rate at very low polymer coverage revealed diffusion limited adsorption. At and above pH 10, the PSS adsorption/desorption was difficult to evaluate. At and above pH 11.5, the hydrolysis of polyamide produced artifacts that prevent any meaningful measurements. This work showed that reflectometry is an interesting analytical tool in the in situ study of the functionalization of organic materials and to investigate the stability of the films produced.     

Preparation and application of poly(alkoxytitanate) as a TiO2 precursor with high storage stability

Titanium dioxide is a basic material of our daily life. Because of its favourable properties, such as harmlessness, chemical stability, photocatalytic activity, or whiteness it is increasingly applied in both micro and nano particles and thin films and coating. One of the available procedures for film forming is the sol–gel technology, an inexpensive low temperature process with wide possibilities to vary film properties by changing the composition of the precursor solution or other parameters. In the paper a new precursor polymer for TiO₂ film-preparation with high storage and processing stabilities is introduced and applied in thin film forming. The new precursor poly(alkoxytitanate) is prepared by a one step, water-free sol–gel method. A smooth TiO₂ film can be prepared using this precursor by spin-coating followed by H₂-plasma curing. Comparing to a common precursor such as Ti(O–iPr)₄, this precursor has a good solubility in different solvents and a much higher storage stability. The easy to modify precursor end groups enable the tailoring of properties regarding to hydrolysis to both TiO₂ particles and films.     

Study of corrosion protection of mild steel by eco-friendly silane sol–gel coating

The effects of dipping duration in the silane solution and the sol pH on the protective performance of an eco-friendly silane sol–gel coating consisting a mixture of tetraethoxysilane, methyltriethoxysilane and glycidyloxypropyltrimethoxysilane applied on mild steel substrate were studied in this paper using electrochemical techniques and surface analysis. In consistency with the data obtained from electrochemical impedance spectroscopy and polarization curves, electrochemical current noise fluctuation analysis, appearance of the power spectral density plots and noise resistance indicated the most efficient sol pH and immersion time in the silane solution. In this regard, field emission type scanning electron microscopy images and water contact angle values revealed impact of the sol pH on the film structure. The enhancement in protective performance of the hybrid coating resulting from optimum immersion in the silane solution with appropriate pH was connected to the film homogeneity and higher cross linking and thickness as well. Moreover, a good trend correlation was observed between the noise resistance and low-frequency impedance modulus data.     

Control of the morphology of nanostructured particles prepared by the spray drying of a nanoparticle sol

The control of the morphology of nanostructured particles prepared by the spray drying of nanoparticle sol was investigated experimentally and the results are qualitatively explained based on available theory. A theoretical analysis indicates that the structural stability of the droplet and the hydrodynamic effects during the drying process play important roles in controlling the morphology of the resulting particles. The size of the sol in the droplet, droplet size, viscosity of droplet, drying temperature, gas flow rate, and addition of surfactant are all crucial parameters that affect the morphology of particles. Experimentally, nanostructured silica particles were prepared from a nanosize silica sol under various preparation conditions. Doughnut-shaped particles can be produced when the droplet size is large, in conjunction with high temperature, high gas flow rate and in the presence of an added surfactant. Appropriate choice of the spray drying method permits control of the particle size and shape, ranging from spheres to ellipsoids as well as doughnut-shaped particles by varying the preparation conditions. The results open a new route to controlling the formation of a wide variety of nanostructured particles.     

Ormocer (ZrO2-PMMA) Films for Stainless Steel Corrosion Protection

The chemical protection of 316 L stainless steel coated with ORMOCER coatings of polymethylmethacrylate (PMMA) and ZrO₂ has been verified. The coatings were dip-coated on the substrates from sols prepared by mixing zirconium propoxide (ZrOC₃H₇)₄, isopropanol (C₃H₇OH), glacial acetic acid (CH₃COOH), polymethylmethacrylate and water under application of ultrasounds. The films were heat treated between 40 and 300°C in air up to 20 h. Their morphology was studied by electron scanning microscopy (SEM). Their anticorrosion behavior was analysed in 0.5M-H₂SO₄ solutions through potentiodynamic polarization curves at room temperature.The influence of the sol preparation, coating composition as well as of the duration and temperature of heat treatments on the corrosion parameters is reported. The films act as geometric blocking layers against the corrosive media and increase the lifetime of the substrate up to a factor 30.     

Coating of Tetraethylorthosilicate (TEOS)/Vinyltriethoxysilane (VTES) Hybrid Solution on Polymer Films

Tetraethylorthosilicate (TEOS)/vinyltriethoxysilane (VTES) hybrid materials were prepared and the hydrolysis and condensation reactions during processing were investigated by means of 29Si NMR solution spectroscopy. The variation of drying characteristics of the coating films was examined with respect to the tetraethylorthosilicate (TEOS)/vinyltriethoxysilane (VTES) ratio, as well as drying temperature, by FT-IR spectroscopy. It is shown that the TO mode of Si–O–Si stretching absorption was enhanced with increasing tetraethylorthosilicate (TEOS) content and drying temperature. Also, the wettability of the coating films on polymer films was independent of the solution composition but enhanced by the precoating of poly(4-hydroxystrene) (PHS) as a wetting agent. The adhesion between the coating and the films was also enhanced when the vinyltriethoxysilane (VTES) content in the coating solution was increased.     

Deposition of silica thin films formed by sol–gel method

Deposition of silica thin films on silicon wafer was investigated by in situ mass measurements with a microbalance configured for dip coating. Mass change was recorded with respect to deposition time when the substrate was fully immersed in the silica sol. Mass gain during deposition was higher than predicted from monolayer coverage of silica nano particles. This implied that deposition was facilitated by gelling of the nanoparticles on the substrate. The rate of deposition was enhanced by increasing the particle concentration in the sol and by decreasing the particle size from 12 to 5 nm. Increasing the salt concentration of the silica sol at constant pH enhanced the deposition of the silica particles. Reducing the pH of the sol from 10 to 6 decreased the deposition rate due to aggregation of the primary silica particles.     

BPA对低温制备锐钛矿型TiO2薄膜表面形貌的控制

采用4,4’-二羟基二苯基丙烷(BPA)作为TiO2薄膜表面形貌控制的模板剂. 将BPA的乙醇溶液与具有锐钛矿晶粒的TiO2溶胶均匀混合制得涂膜液, 采用浸渍提拉法制备薄膜; 用无水乙醇将薄膜中的BPA选择性溶解去除, 实现了低温下锐钛矿型TiO2薄膜的制备及其表面形貌的调控. 采用SEM考察了TiO2溶胶用量、BPA用量、以及无水乙醇用量等因素对TiO2薄膜表面形貌的影响, 并对其控制机理进行了探讨. 结果表明, 涂膜液的组成会影响到湿膜烘干过程中粒子的迁移和聚集, 从而改变TiO2与BPA 在薄膜表面的分布状态, 最终对TiO2薄膜的表面形貌产生影响. 随BPA浓度的降低,其影响逐渐由薄膜内部转向薄膜的表面区域. 而低TiO2胶粒浓度和高乙醇含量则有利于TiO2薄膜产生粗糙的形貌或多孔性的结构.