Silica Sol-Gel Coatings on Metals Produced by EPD

The objective of this work has been to combine the sol-gel method and the electrophoretic deposition (EPD) process to prepare thick coatings onto metallic substrates. Two different routes were used for preparing the sol-gel silica suspensions. On one hand, silica particulate sols were obtained by basic catalysis of alkoxides and alkylalkoxides. On the other, silica suspensions were prepared by adding a commercial colloidal silica sol to an organic-inorganic acid catalysed silica sol. The properties of the suspension and the physical parameters associated to EPD (current density, potential, electric field and deposition time) were studied. Crack-free deposits up to 20 m were obtained after drying and crack-free glass-like coatings of 12 m after sintering at 500°C for 30 minutes. The electrochemical behaviour of these coatings was evaluated by potentiodynamic methods, showing an excellent behaviour against corrosion.     

SiO2纳米粒子对溶胶凝胶涂层性能的影响

在高强钢表面制备了防护性溶胶凝胶涂层,并研究了不同浓度二氧化硅纳米粒子的加入对于涂层形貌、耐蚀性和硬度的影响。采用扫描电子显微镜(SEM)和电子能谱(EDS)观察了涂层的微观结构和成分;采用显微硬度计测试了涂层的硬度;采用电化学方法研究了二氧化硅纳米粒子的浓度对于涂层耐蚀性能的影响;采用傅里叶红外光谱研究涂层的化学结构,进而探讨了二氧化硅纳米粒子对于涂层的强化机理。结果显示涂层加入二氧化硅纳米粒子的最佳浓度为500 mg.L-1,此条件下的涂层表面均匀致密,有较高的硬度并且在3.5%NaCl溶液中体现出较好的耐蚀作用。纳米粒子在溶胶中反应形成活性羟基基团并与硅烷发生反应生成空间网状结构,从而强化涂层。     

Spectroscopic Study of Cerium-Doped Silica Gel Monoliths and Their Densified Derivatives

Cerium is exploited as a probe cation for elucidating the structure of an alkoxide-derived silica gel and its progressive evolution to a glass network as a function of heat-treatment up to 1000°C. At intermediate temperatures, the host structure exhibits inhomogeneity due to insufficient formation of siloxane bonds, which is reflected by at least two different sites and co-ordination spheres (termed “high” and “low” water ligation) for cerium. This is proved by the response of the gels heated up to 700°C to rehydration. Further formation of Si−O−Si network (900°C) leads to the destruction of the “high water” sites of cerium and progression towards a glassy structure. It is, however, only after heat-treatment at 1000°C that a dense silica glass network, not responding to rehydration, is finally obtained with cerium ions embedded in it.     

Bioactive Sol-Gel Coatings for Orthopaedic Prosthesis

Sol-gel materials have been proposed in last years for clinical applications. In this work, bioactive sol-gel coatings were prepared from suspensions of up to 25% wt. of bioactive glass (CaO·SiO₂·P₂O₅) particles in a hybrid sol obtained from TEOS and MTES. Thick dip-coatings showed in vitro bioactivity after a few days, but glass-particles dissolution promotes a slight reduction in the corrosion resistance. In order to overpass this problem, a two-stage sol-gel coating system that includes a first SiO₂ hybrid film, acting as barrier against corrosion, and an external bioactive layer from glass particle suspension is proposed. The obtained samples revealed significant improvement in their electrochemical behaviour, and showed in vitro bioactivity.     

Bioactive and Protective Sol-Gel Coatings on Metals for Orthopaedic Prostheses

The aim of this work has been the preparation and evaluation of sol-gel coatings for clinical applications. Research was focussed in the development of highly corrosion resistant and/or bioactive sol-gel coatings onto AISI 316L stainless steel. Hybrid SiO₂ sol-gel coatings inhibited corrosion and Fe diffusion, although no signal of bioactivity was detected. The inclusion of Ca- and P-alcoxides in the sol composition did not promote bioactivity. Bioactive coatings were obtained from suspensions prepared by adding glass (CaO·SiO₂·P₂O₅) particles to an hybrid organic-inorganic SiO₂ sol. The dissolution of glass particles promoted in vitro induction of apatite along with a slight reduction in the corrosion resistance of coated pieces. By combining an inner SiO₂ hybrid film acting as barrier against corrosion with an outer coating containing bioactive glass particles, a significant improvement in the electrochemical behaviour was observed. This double-layered coating showed in vitro signals of bioactivity, and preliminary in vivo tests gave promising results.     

Sol-Gel Derived Calcium Phosphate Coatings for Biomedical Applications

Hydroxyapatite (HA) coatings have received considerable attention because they exhibit bone bonding capabilities. Unfortunately the common forms of coating production result in cracking and degradation of HA due to the thickness of the coatings and the elevated temperatures employed. This study demonstrates the production of sub-micron, crack-free calcium phosphate coatings on quartz glass substrates using a sol-gel dip-coating technique and firing temperatures below 1000°C.Coatings fired at 1000°C comprised a mixture of hydroxyapatite (HA) and tricalcium phosphate (TCP). XPS analysis of the coating surface showed that the Ca/P ratio lay in the range 1.5–1.67, and that there was a contribution from carbon in the form of carbonate.It is proposed that the sol-gel coatings comprising a resorbable (TCP) and an insoluble (HA) phase have potential benefits in certain implant applications.     

Sol-Gel Coatings for the Protection of Brass and Bronze

The effectiveness of sol-gel Ormosil coatings as barriers coatings has already been demonstrated, and it is natural to assume that such coatings can play a unique role in art conservation, where object corrosion and decay are often a major issue. The main feature of ormosil coatings that would make them preferable to polymers is their potentially higher stability to ultra-violet radiation, controlled porosity and good adhesion to many different substrates. The permeability to various gases can also be tailored with changes in the chemical structure. In previous work, we have applied the sol-gel process as part of a multiplayer coating in the conservation of the Last Judgment mosaic in Prague. In the present work, we explore the use of sol-gel organic-inorganic hybrid coatings on various copper alloy substrates frequently encountered in art conservation.     

Sol-Gel Chemistry of Tantala HR Coatings: Structure and Laser-Damage Resistance

Sol-gel processing of Ta(OC₂H₅)₅ to produce high reflective and high refractive index (HR) tantala coatings has been followed by infrared spectroscopy (FTIR), where in the presence of ethanoic acid, both chelation and hydrolysis reactions co-exist, depending on the preparative parameters. However, most of the precursor was found to convert into an amorphous tantala sol and finally a gel. Transmission electron microscopy (TEM) and light-scattering showed that the primary sol particles (whose size was about 5 nm) aggregated into clusters up to 60–80 nm via different linkages: ring-like, cross-linked and colloidal structures. Thermal analysis-X-ray diffraction (TGA-XRD) indicated that the gel did not crystallise below 700 K. Tantala films (0.3 μm thick; refractive index of 1.7) were prepared by spin-coating of these sols and had properties closely related to the sol structure.     

Fluorescence of Pyranine in Sol-Gel Based Silica and Hybrid Thin Films

The sensitivity of the pyranine fluorescence to protonation/deprotonation is used to follow modifications in cured sol-gel thin films. The acid concentration in the sol-gel solution is varied for TEOS-based coatings and a series of organically modified silanes Si(OR)₃R’ are added to the TEOS solution. The concentration of the organically modified silane is varied as well as the chain length of the alkylgroup (R’). The stationary fluorescence measurements show that the equilibrium between the protonated and the deprotonated form of pyranine changes depending on the type of silica matrix. The deprotonated form is dominant in the cured SiO₂ films and the protonation/deprotonation ratio of pyranine is constant for the different acid concentrations used. The protonated form becomes dominant as the concentration of Si(OR)₃R’ is increased and as the alkyl chain length (R’) of the organically modified silanes is augmented. Emission anisotropy measurements of pyranine in the same coatings show that the rotational freedom of the molecule changes due to modifications in the cages for the TEOS-based coatings. These modifications are produced by the acid concentration used to prepare the coatings. An increase in the rotational freedom of pyranine is observed in the TEOS-Si(OR)₃R’ systems.     

疏水性对溶胶-凝胶SiO2薄膜抗真空污染及抗激光损伤能力的影响

以正硅酸乙酯作为前驱体,利用碱催化方式制备了SiO2溶胶,通过在溶胶中添加含疏水基团(-CH3)的六甲基二硅氮烷(HMDS)对溶胶进行改性,使用添加不同物质的量比HMDS改性后的溶胶用提拉法在K9基片上镀膜,获得了具有疏水性能的SiO2薄膜。采用自制接触角测量仪、紫外-可见-近红外分光光度计研究了薄膜的水接触角和透过率。测试了薄膜的激光损伤阈值,并观察了激光辐照后薄膜的损伤形貌。通过真空污染实验对薄膜的抗污染能力及抗激光损伤能力进行了研究。实验结果表明:经疏水改性的溶胶所镀制的薄膜激光损伤阈值由未改性样品的24.3 J·cm-2增加到37 J·cm-2(1 064 nm,10 ns),且抗真空污染能力大大加强:在真空环境下保存168 h后,未改性样品的峰值透过率下降了2%,而疏水改性后的样品峰值透过率仅下降了0.25%,并保持了较高的激光损伤阈值(30.8 J·cm-2)。     

表面活性剂辅助酸催化溶胶-凝胶法制备高强度超亲水二氧化硅减反增透纳米粒子涂层

以正硅酸乙酯(TEOS)、十六烷基三甲基溴化氨(CTAB)、盐酸(HCl)、乙醇和水为原料,通过溶胶-凝胶法提拉涂膜,再经700 ℃快速淬火200 s,制备了二氧化硅（SiO2）纳米粒子涂层。 研究了CTAB浓度、提拉速度、停留时间和提拉涂膜次数对透射率的影响,结果表明,当CTAB质量分数为2.5%,提拉速度为100 mm/min,停留时间为60 s,提拉涂膜1次得到的SiO2纳米粒子涂层透射率最高,可达95.9%。 该涂层具备超亲水性并能耐受6H铅笔刮痕测试。 实验还表明,在SiO2溶胶液中加入CTAB,通过其与TEOS部分水解生成的物种的相互作用,可以改善酸性催化条件下形成的SiO2溶胶的微观结构,从而提高了涂层的透射率和亲水性。     

Effect of Sintering Temperature on the Corrosion and Wear Behavior of Protective SiO2-Based Sol-Gel Coatings

Sol-gel hybrid organic-inorganic and inorganic SiO₂-based protective coatings with and without added 3 m glass particles were developed and tested for their corrosion and wear behavior of an stainless steel substrate (AISI316L). The corrosion resistance greatly increases by incorporating glass particles in the sols. The incorporation of particles in the coatings allows the synthesis of thicker crack-free coatings. On the other hand, the corrosion resistance increases for coatings with a higher organic content obtained at lower sintering temperature. These coatings are also highly stable in saline aqueous solutions. However, the wear resistance is badly affected by the hybrid character of the SiO₂ matrix. The optimum coating process in terms of corrosion and wear resistance, appears to be a hybrid system with a dense SiO₂ network achieved at intermediate sintering temperatures.     

疏水性对溶胶-凝胶SiO2薄膜抗真空污染及抗激光损伤能力的影响

以正硅酸乙酯作为前驱体, 利用碱催化方式制备了SiO₂溶胶, 通过在溶胶中添加含疏水基团(-CH₃)的六甲基二硅氮烷(HMDS)对溶胶进行改性, 使用添加不同物质的量比HMDS改性后的溶胶用提拉法在K9基片上镀膜, 获得了具有疏水性能的SiO₂薄膜。采用自制接触角测量仪、紫外-可见-近红外分光光度计研究了薄膜的水接触角和透过率。测试了薄膜的激光损伤阈值, 并观察了激光辐照后薄膜的损伤形貌。通过真空污染实验对薄膜的抗污染能力及抗激光损伤能力进行了研究。实验结果表明:经疏水改性的溶胶所镀制的薄膜激光损伤阈值由未改性样品的24.3 J·cm^-2增加到37 J·cm^-2(1 064 nm, 10 ns), 且抗真空污染能力大大加强:在真空环境下保存168 h后, 未改性样品的峰值透过率下降了2%, 而疏水改性后的样品峰值透过率仅下降了0.25%, 并保持了较高的激光损伤阈值(30.8 J·cm^-2)。     

X-Ray Spectroscopic Investigation of the Zr-Site in Thin Film Sol-Gel Surface Preparations

X-ray photoelectron spectroscopy (XPS) and x-ray absorption spectroscopy (XAS) measurements were made on thin film (1000 Å) sol-gel adhesion promoting surface treatments. These silicon/zirconium-containing sol-gel coatings are possible replacement processes for traditional surface preparations that use environmentally undesirable and potentially toxic materials. The sol-gels were waterborne mixtures formulated with tetra-n-propoxyzirconium (TPOZ) and a silane, either 3-glycidoxypropyl-trimethoxysilane (GTMS) or 3-aminopropyl-triethoxysilane (APS). Results show that dried sol-gel powders formulated with TPOZ or TPOZ + GTMS have longer Zr—O bond lengths (2.18 Å, CN 7 or 8) than the TPOZ + silane + metal substrate samples (2.10 Å, CN 6). The fraction (+/– 0.10) of Zr in a short bonded 6-fold site is highest (0.80) for TPOZ + (APS or GTMS) on (Ti or Al), at an intermediate value (0.40) for TPOZ on Ti and low (0.10) for the powders. For sol-gels deposited on a metal substrate, there are indications of a chemical bond between the thin film sol-gel and the metal substrate. The TPOZ + APS coatings on Ti data suggest that this Zr—O—Ti bond is present with a Zr—Ti separation of 3.5 Å. Only subtle differences were observed in the near-neighbor bonding due to curing treatment variations from room temperature to 125°C, alloy substrate variations (Ti-6Al-4V/Al 2024), and age of the deposited sol-gel coating (up to 1 year).     

Nitro-Porphyrin Entrapped in a Silica Matrix by Sol-Gel Methodology

This work describes the preparation of the iron (III) porphyrin, FeTDCNO₂, entrapped in a silica matrix in the form of powder (FePD) or thin film using the sol-gel process. The films were obtained from sols using the dip-coating technique. The variables involved in the FePD preparation were analysed by a fractional factorial design with resolution 5, designated by 2 _V ^{5 – 1}. The variables which present a positive effect and maximise the loading of the studied ironporphyrin on the FePD material are solvent, water volume and reaction time. The utilization of pyridine or imidazole as template does not affect the preparation of the FePD material. The UV-visible absorption spectra of all prepared materials present the characteristic Soret band of ironporphyrins at 419–420 nm.The materials were analysed by thermogravimetric analysis, isotherm of nitrogen adsorption, ²⁹Si NMR and scanning electron micrograph. The catalytic performance of FePD-imidazole on the epoxidation of z-cyclooctene with iodosylbenzene is similar to that of FeTDCNO₂ in homogeneous solution (60 and 52%).     

Auto-Organisation in Silica-Based Organic-Inorganic Gels Obtained by Sol-Gel Process

A new type of hybrid material is prepared through sol-gel processing by the polycondensation of (MeO)₃Si–R–Si(OMe)₃ units containing a rigid organic anisotropic group R. The hybrid covalently bounded organic-inorganic gel shows an unexpected structural birefringence n (n = 2 × 10^–3). This birefringence is induced by a strain field anisotropy during gel aging as revealed by simultaneous dynamic light scattering and birefringence measurements. To better address the role of the strain field, we use a free interface sol-gel/air to control strain anisotropy and to measure the gel optical axis and its birefringence. We find that the birefringence is associated to a long-range orientational order of organic moieties induced by the strain anisotropy during the gel aging.     

Industrial Application of Hybrid Sol-Gel Coatings for the Decoration of Crystal Glassware

The coloration of glass via melting techniques presents some unique problems with respect to the reproducibility, toxicology and economics of certain colors, especially if the market demands are highly variable. This is also the case for consumer products such as crystal glass and tableware. Traditionally, the decoration of crystal glasses is performed by laborious manual techniques, which are costly and do not meet modern market requirements. Alternatively, spraying of colored lacquers is a highly flexible and valuable tool for the development of new products. Sol-gel type hybrid coatings provide several advantages compared to conventional organic systems like high abrasion resistance, almost perfect adhesion, refractive index matching and sufficient stability in dishwashing procedures. The solubility of organic dyes in the hybrid matrix is sufficient for intense colors even at rather low layer thicknesses, which on the other hand convey the high brilliance of the base material. The development of transparent, translucent and opaque hybrid coatings for crystal glass has been completed in the last few years and the production of partially coated articles has started recently. The synthesis and properties of the coating material are reviewed and the industrial process and first market results are also outlined.     

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.     

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.