Adhesion of Sol-Gel-Derived Organic-Inorganic Hybrid Coatings on Polyester

Inorganic coatings, including metal-oxide coatings, provide polymer surfaces with excellent abrasion and wear resistance, and protection against environmental degradation. However, one drawback associated with the incorporation of such ceramic coatings to polymeric materials is the adhesion characteristic at the ceramic-polymer interface. In this paper, two strategies for adhesion enhancement of ceramic coatings on polymer substrates were proposed: (1) formation of chemical bonds through surface condensation reactions, and (2) development of interlocked ceramic and polymeric networks through diffusion of alkoxide precursors. The current research has focused on the adhesion of sol-gel-derived organic-inorganic hybrid coatings on polyester by forming chemical bonds between the polymer substrate and the hybrid coatings, as well as developing interlocked polymeric and inorganic networks at the interface. Contact angle, wettability tests, and chemicalanalysis were done to verify the effectiveness of the adhesion of organic-inorganic hybrid coatings on polyester substrates. In addition, dry and wet thermal cycling tests were done to analyze the adhesion behavior of the hybrid coatings on polyester, followed by microscopy examination. It was found that although both approaches resulted in excellent adhesion of hybrid coatings on polyester, adhesion with interlocked ceramic and polymeric networks was far better than that with chemical bonds in the presence of water at elevated temperatures.     

Investigation of Glass-Like Sol-Gel Coatings for Corrosion Protection of Stainless Steel Against Liquid and Gaseous Attack

Glass-like sol-gel coatings have been investigated as corrosion protective coatings on stainless steel. Magnesium- and borosilicate coatings with thickness of about 100–700 nm and methyl-modified SiO2 coatings with a thickness of about 2 m were deposited on stainless steel plates by dip-coating. The coatings were densified between 400°C and 500°C in different atmospheres (N2, air) for 1 h. The corrosion protection against gaseous attack was investigated by accelerated corrosion tests, at 800°C in air for 1 h. A corrosion protection factor was calculated from the relation Fe/Fe2O3, determined by XRD on the surface of coated and uncoated samples. Methyl-modified SiO2 coatings showed a protection factor, which was 2 orders of magnitude higher than for the other coatings. Electrochemical investigations were performed on samples submerged in a NaCl solution for 200 h. The corrosion propagation, polarization resistance and impedance vector were measured. For accelerated corrosion tests, polarization intensity curves were determined for high potentials of up to 1 V. Again excellent results were obtained for the methyl-modified SiO2 coatings, which remained passive for 200 h. Results of the salt spray corrosion test, however, showed no corrosion protection by the sol-gel coatings. After 2000 h in the salt spray chamber the steel was corroded and the coatings peeled off. It is concluded that for the further development of these coatings an improved interfacial passivation will be required.     

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.     

Synthesis and Properties of Cerium and Titanium Oxide Thin Coatings for Corrosion Protection of 304 Stainless Steel

Powders and thin coatings of ceria and titania were synthesized from aqueous and solvent-based precursors. Thin coatings were deposited on polished 304 stainless steel coupons by dipping them in the appropriate sol-gel oxide precursors. The coatings were subsequently densified and crystallized at several hundreds of degrees. It was possible to obtain dense titania coatings by applying thin coatings of cerium dioxide prior to titania on stainless steel substrates. Underlayer ceria coatings proved to be pivotal in obtaining dense titania coatings and preserving the integrity of the stainless steel while going through the high temperature treatments. The effect of processing parameters such as the atmosphere of heat-treatment, and temperature on the microstructure and crystal structure of the films and powders of ceria and titania was investigated. X-ray diffraction was used to identify the crystal structure of films and powders upon heat-treatment. Electrochemical measurements in NaCl, and analytical techniques such as SEM and EDX were used to evaluate the corrosion performance and pitting morphology of coated samples. A composite coating of ceria and titania was able to prevent crevice corrosion and increase the pitting resistance of the 304 stainless steel relative to the uncoated substrate.     

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.     

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.     

Sol-Gel Coatings on Non-Oxide Planar Substrates and Fibers: A Protection Barrier Against Oxidation and Corrosion

Sol-gel coatings on non-oxide substrates can be used to prevent high temperature degradation and to improve wet corrosion resistance. Alumina coatings were investigated. The starting precursor was aluminium sec-butoxide, modified with chelating ligands such as 2,4-pentanedione or acrylic acid to prevent its precipitation in the presence of water. Stainless steel plates and Hi-Nicalon SiC fibers are often utilized in different kinds of applications and thus were selected as substrates. Thin films were deposited from the modified alkoxide solutions using dip-coating techniques. The parameters governing the process such as the aging of the sols, the viscosity, the withdrawal rate and the thermal treatment were investigated. The films were characterized (morphology, thickness) and showed an interesting behaviour as protection barrier in an aggressive medium.     

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.     

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.     

LC4铝合金表面电泳沉积硅锆有机-无机杂化涂层的制备及性能

采用阴极电泳沉积的方法在LC4铝合金表面制备硅锆有机-无机杂化涂层, 并探讨了电泳沉积条件对涂层形貌、结构以及耐蚀性的影响. 采用纳米粒度仪检测了不同硅锆杂化溶胶的zeta电位; 采用扫描电子显微镜(SEM)和原子力显微镜(AFM)观察了涂层的表面微观形貌和粗糙程度; 采用傅里叶红外光谱(FTIR)研究了涂层的化学结构; 采用电化学方法研究了沉积电压对涂层耐蚀性能的影响, 进而探讨了电泳沉积增强杂化涂层耐蚀性的机理. 结果显示沉积体系的pH为1.6、沉积电压为5 V时为最佳的沉积条件, 所获得的硅锆有机-无机杂化涂层表面均匀致密性最好, 粗糙程度和耐蚀性都得到了明显的改善, 在3.5% NaCl溶液中体现出较好的耐蚀作用.     

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.     

Long-Term Protection of the Last Judgment Mosaic in Prague

A sol-gel coating was used in the long-term protection of the 14th Century mosaic situated above the gates of St. Vitus cathedral, in the center of Prague Castle. The choice of a sol-gel coating is the result of a research effort involving both on-site testing in Prague and accelerated ageing of various polymers and sol-gel materials in the laboratory. The coating selected for treatment of the entire 13 m × 10 m mosaic is a multi-layer system in which an organic-inorganic sol-gel layer is placed between the glass substrate and a fluoropolymer coating. This coating combination performed very well in an accelerated weathering chamber as well as during onsite testing. Since the top layer is scheduled to be removed and re-applied periodically, it is hoped that this concept will allow long term protection to the largest outdoors mosaic north of the Alps. On-site application of the coatings on the entire mosaic started in 1998 and will be completed in 2000.     

新型光敏聚酰亚胺/SiO2杂化材料的制备与性能研究

通过溶胶－凝胶法制备了一种新型的光敏聚酰亚胺／二氧化硅杂化材料。研究表明当ＳｉＯ２的含量≤１０ｗｔ％时杂化材料除了保持光敏聚酰亚胺原有的感光性能外其热稳定性能、力学性能以及与基底的粘附性能均有明显地提高,同时材料的热膨胀系数也显著地降低。     

Thermoset Alkyd-Acrylic Hybrid Emulsions for Coatings

Alkyd acrylic hybrid emulsions can offer cost/performance advantages over common 1K coatings such as polyurethane dispersions (PUDs), acrylic emulsions and blends. Hybrid emulsions with different ratios of alkyd resin to acrylic monomers were synthesized. Emulsion with resin-to monomer ratio of 1:1 (wt/wt) with total solids as high as 50% had a shelf stability of more than 8 months. Morphology of hybrid emulsions was studied by scanning electron microscopy. Hybrid emulsions were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Films obtained from the hybrid emulsions were found to be homogeneous and exhibited excellent thermal and coating properties.     

有机-无机杂化溶胶-凝胶涂层对不锈钢毛细管柱的脱活作用研究

 用甲基三乙氧基硅烷和四乙氧基硅烷水解缩合后形成的有机 无机杂化溶胶 凝胶 (sol gel)涂层对国产气相用不锈钢毛细管柱进行脱活。通过气相法研究了不同老化温度下所得脱活涂层的行为。结果表明这种涂层不但对不锈钢柱内壁活性点有很好的遮盖作用 ,而且本身具有相当的分离能力。在 2 5 0℃下老化的涂层可使碳原子数在 12以下的正构烷烃达到基线分离 ,与未用涂层的不锈钢裸柱相比 ,吸附活性大大降低 ;但随着老化温度的升高 ,涂层在缩聚老化过程中产生不均匀微孔 ,对被分离物的作用力加强。     

Sol-gel ZrO2 coatings for chemical protection of stainless steel

ZrO₂ coatings deposited on 316 L stainless steel sheets were synthesized by sol-gel method using Zr(OC₃H₇)₄ as precursor and isopropanol, glacial acetic acid, and water as solvents for application with ultrasounds. Different solutions for dip-coating were prepared with compositions varying between 0.025 and 0.9 mol/dm³ of ZrO₂. X-ray diffraction shows that the films densified at 800°C are crystalline with a tetragonal structure. The thickness of the coatings varied from 0.35–0.75 m. The influence of the ZrO₂ coatings on the corrosion behavior of stainless steel substrates in aqueous NaCl was studied through potentiodynamic polarization curves at 1 mV/s. The values of the electrochemical parameters allow for an explanation of the role of the films in the increased resistance of steel against corrosion in moderately aggressive environments.     

SNAP溶胶组成对镁合金涂层耐蚀性的影响

本文利用纳米自组装颗粒工艺(SNAP)在AZ31B镁合金表面制备了防腐涂层。通过透射电镜(TEM)和扫描电镜(SEM)观察及电化学阻抗谱(EIS)、电导率测试等,对SNAP溶胶的纳米粒子形态和电导率,以及SNAP涂层的表面形貌和耐蚀性进行了测试,研究了不同含量的有机硅烷前躯体3-缩水甘油醚丙基三甲氧基硅烷(GPTMS)和正硅酸乙酯基硅烷(TEOS)、溶剂水、助溶剂无水乙醇、交联剂三乙烯四胺(TETA)等对镁合金SNAP涂层耐蚀性的影响。研究结果表明,随着溶胶中TEOS和TETA含量的增大,镁合金涂层耐蚀性呈先增大后减小的趋势;随着溶胶中水含量的增大,镁合金涂层耐蚀性提高;溶胶中无水乙醇的含量较低时,对镁合金涂层耐蚀性的影响较小。     

Hybrid Organic-Inorganic Sol-Gel Materials Based on Epoxy-Amine Systems

Understanding the synthesis-structure-properties relationship of hybrid organic-inorganic materials is an important and fundamental task to develop a new generation of highly performing systems for the new needs of nanotechnologies. This issue is, also, important to improve the properties of hybrids when used in applications where nanoscale control is not a fundamental request. In this article, a short overview of epoxy amine sol-gel hybrids is reported. The synthesis of these materials has a large flexibility to allow the fabrication of a wide group of hybrids with different structures and properties, whose applications are ranging from non-linear optics to adhesive and protective coatings.     

聚苯胺对新型杂化透明导电薄膜制备和性能的影响

以聚苯胺和掺锑的氧化锡作为主要原料, 采用溶胶-凝胶法制备了新型有机-无机杂化透明导电薄膜. 薄膜的可见光透过率为85%以上, 电导率达到10⁰～10¹ S•cm^－1. 研究了聚苯胺含量的变化对浸涂液粘度、薄膜结构、光透过率、电导率的影响. 随着聚苯胺引入量的增加, 薄膜的电导率、可见光透过率均有所增大. 浸涂液的粘度可在长达25天的时间内保持稳定, 很适于浸涂工艺. 扫描电镜照片显示, 薄膜比较致密、均匀, 厚度为250 nm左右.