溶胶-凝胶/环氧杂化涂料的应用

溶胶-凝胶/环氧杂化涂料的配方已经进行了研究,杂化涂料具有更强的机械强度(如硬度),更加耐磨蚀。当固化温度提高到80℃,全部研究的杂化涂料都能通过湿性黏结试验,但在室温下固化时仅有部分的杂化涂料通过湿性黏结试验。多数杂化涂料在室温下固化时对水的敏感性问题尚待解决。     

Testing and evaluation of nonchromated coating systems for aerospace applications

The advanced corrosion resistant aircraft coatings program (ACRAC) is part of the Air Force strategy to improve performance and reduce environmental impact of coatings used on Air Force weapon systems. The program addresses the Air Force near and mid-term strategies to eliminate chromate corrosion inhibitors and reduce steps in the outer mold line coating process. Evaluation of the coating process (surface preparation, conversion coating, primer, topcoat) as a system is a key feature of the ACRAC program. Results to date indicate that the current-state-of-the-art nonchromated coating systems are significantly less effective than those with chromate. A chromate conversion coating is required for the nonchromate primer system to meet minimum requirements. Sol–gel-process based conversion coatings can replace chromate conversion coatings provided a chromated primer is used. Several approaches to incorporating inhibitors into sol–gel coatings are discussed. Electrochemical methods for testing coating performance are discussed and a new procedure based on impedance spectroscopy for evaluating active damage repair is presented.     

Ternary evaluation of UV-curable seed oil inorganic/organic hybrid coatings using experimental design

Inorganic/organic hybrid coatings were prepared using epoxidized linseed oil with combinations of the two sol–gel precursors (titanium(IV) isopropoxide, tetraethyl orthosilicate), and a telechelic silicate based on a modified oligomeric caprolactone. The coatings were UV-cured with sulfonium initiators which concomitantly cured the epoxy functional organic phase and the sol–gel inorganic phase to form a co-continuous inorganic/organic system. A ternary experimental design was employed to elucidate the influence of inorganic modifier on the mechanical properties of the inorganic/organic hybrid coatings. Small angle X-ray scattering (SAXS) was used to evaluate radius of gyration of the metal-oxo-cluster. Various coating properties, such as hardness, impact resistance, adhesion, solvent resistance, and surface energy were investigated as a function of sol–gel precursors. Inorganic/organic hybrid coatings containing both tetraethyl orthosilicate and the modified caprolactone resulted in improved hardness and solvent resistance with no loss of impact strength. The inclusion of titanium(IV) isopropoxide in to the systems resulted in a systematic reduction in the coatings properties. This was attributed to inhibition of the organic crosslinking process as a consequence of absorption of ultraviolet light by the titanium-oxo-clusters.     

An organically modified zirconate film as a corrosion-resistant treatment for aluminum 2024-T3

Current coating systems for aircraft corrosion protection are based on a traditional chromate surface treatment, primer, and topcoat. The Air Force is seeking environmentally benign corrosion-resistant surface treatments for aluminum-skinned aircraft as a replacement for environmentally hazardous surface treatments involving chromates. Performance of replacement treatments must be able to satisfy the durability needed for dramatically extended lifetimes, be compatible with present and future environmental requirements, and be easily integrated into current primer/topcoat paint systems.

Organically modified zirconate sol–gel films were investigated as an environmentally compliant replacement for chromated surface treatments, which included functionalized components to tailor the chemistry at both the aluminum oxide substrate/surface treatment interface and the surface treatment/topcoat interface. Sol–gel films were applied to aluminum 2024-T3 alloy coupons, and the resulting film chemistry was investigated. FTIR was used to identify organic components in the film and X-ray photoelectron spectroscopy was used to investigate the interface chemistry. The result of the chemically modified sol–gel synthesis was a coating in which a concentration gradient was formed at the surface, which is discussed. The corrosion protection attributes of these films was also studied and the electrochemical evaluation of sol–gel films will be discussed, both as stand-alone coatings and as part of a full coating system.

Organically modified sol–gels exhibited significantly better protection in terms of barrier properties in comparison to a typical chromate-based processes. The resulting data from evaluations of sol–gel produced coatings show promise towards the goal of producing a robust chemical interaction/bonding of such corrosion-resistant coatings on the surface of aluminum-skinned aircraft without the use of environmentally hazardous chromate agents.     

Nanostructured sol–gel derived conversion coatings based on epoxy- and amino-silanes

Inorganic/organic hybrid conversion surface coatings for long-term protection of aluminum alloys against atmospheric corrosion have been developed based on a unique self-assembled nanophase particle (SNAP) coating process. Nano-particles with peripheral epoxy functional groups are pre-formed in an aqueous sol–gel process and then assembled and crosslinked upon application on the substrate surface. Mono-, di-, and tri-functional amino-silanes have been used as crosslinking agents. Corrosion resistance properties of these hybrid nanocomposite coatings studied by a variety of electrochemical testing methods including electrochemical impedance spectroscopy, scanning vibrating electrode technique, and potentiodynamic scan method, indicate excellent barrier protection performance of the coatings. For comparison, coatings crosslinked with amino-silanes offer significant improvement in coating performance over the previously described SNAP formulations with a conventional amine crosslinker—diethylenetriamine.     

Silica based organic–inorganic hybrid nanocomposite coatings for corrosion protection

Silica based organic–inorganic hybrid nanocomposite coatings have been developed for corrosion protection of 1050 aluminum alloys by dip coatings technique. The hybrid sols were prepared by hydrolysis and condensation of 3-glycidoxypropyl-trimethoxysilane (GPTMS) and tetramethoxy silane (TMOS) in the presence of an acidic catalyst and bisphenol A (BPA) as cross-linking agent. Such prepared hybrid coatings were found to be relatively dense, uniform and defect free. Structural characterization of the hybrid coatings were performed using optical microscopy, scanning electron microscopy (SEM) and attenuated total reflectance-infrared (ATR-IR) spectroscopy. Corrosion resistance properties of the hybrid sol–gel coatings were studied by potentiodynamic scanning (PDS) and salt spray testing methods. The results indicate excellent barrier protection performance of the coatings. In addition, the effect of molar ratio of GPTMS–BPA (silane content) on corrosion resistance of the coatings was investigated. The PDS results demonstrated that the corrosion resistance of hybrid coatings improved by decreasing of silane content.     

Real time mapping of corrosion activity under coatings

Current accelerated testing of aircraft coating systems for corrosion protection relies heavily on salt spray methods. Electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and electrochemical noise methods (ENM) provide insight into the global properties of a coating system, and both techniques are being used on a limited basis. However, there is a need to investigate corrosion events with greater spatial resolution under coatings at the metal/coating interface. Such corrosion activity may be related to coating defects and variations in the surface chemistry of the underlying metal.

The scanning vibrating electrode technique (SVET) has been developed to allow high spatial resolution investigation of localized corrosion activity that may be associated with coating defects or galvanic coupled regions of the metal surface. The SVET offers high resolution in current measurements of the order of 0.5 μA/cm² and is able to detect in-situ initiation and progress of corrosion activity under a protective coating. Using the SVET, minute variations in d.c. current associated with localized corrosion activity are detected and used to map both anodic and cathodic corrosion activities in a localized area. The difference in initial corrosion activity under various coatings can be correlated to the performance life of the coatings. The application of SVET to aircraft coatings and corrosion is reported to demonstrate the utility of this important new electrochemical tool.

In the current study, the SVET was used to discriminate the corrosion protection performance of selected sol–gel based coating systems. Sol–gel based surface treatments are being developed as part of an environmentally compliant coating system alternative to the currently used chromate-based systems. The SVET results are compared with data obtained from chromium inhibition coating systems. The SVET analyses are compared with electrochemical impedance measurements. The comparison of such data will provide the basis to adopt SVET measurements as an early performance discriminator for newly developed coating systems.     

Transparent UV curable antistatic hybrid coatings on polycarbonate prepared by the sol–gel method

UV curable, hard, and transparent organic–inorganic hybrid coatings with covalent links between the inorganic and the organic networks were prepared by the sol–gel method. These hybrid coating materials were synthesised using a commercially available, acrylate end-capped polyurethane oligomeric resin, hexanedioldiacrylate (HDDA) as a reactive solvent, 3-(trimethoxysilyl)propoxymethacrylate (MPTMS) as a coupling agent between the organic and inorganic phase, and a metal alkoxide, tetraethylorthosilicate (TEOS). The materials were applied onto polycarbonate sheets and UV cured, followed by a thermal treatment to give a transparent coating with a good adhesion and abrasion resistance. The high transmission and the thermogravimetric behaviour indicate the presence of a nanoscale hybrid composition. In a taber abrasion test, uncoated polycarbonate sheets exhibit a 48% decrease in light transmittance at 633 nm after 300 wear cycles, whereas the hybrid coating system containing 10 wt% silica shows only 10% decrease in light transmittance. For obtaining antistatic coatings, an intrinsically conductive polymer (ICP) was added to the optimised coating formulation. It is shown that the surface resistivity of the organic–inorganic hybrid coating can be reduced from 10¹⁶ to 10⁶ Ω for a high concentration of ICP in the coating formulation.     

Protective space coatings: a ceramer approach for nanoscale materials

There is a concerted and focused push to develop protective space coatings for vehicles in low earth and geosynchronous orbit. The space environment is not suitable for organic materials due to atomic oxygen, high energy particles, and deep UV light being able to degrade polymeric organic resins. An inorganic/organic hybrid coating, known as a ceramer, will be fabricated using a polysiloxane binder and nanophase silicon/metal-oxo-clusters derived from sol–gel precursors. The binder of the coating will be a substituted polysiloxane terminated with a cyclohexyl epoxide. The cyclohexyl epoxide will be cured at ambient temperature via a cationic UV curing mechanism. PDSC will also be used to investigate the effects of temperature, UV light intensity, sol–gel precursor concentration, and exposure time have on the rate of polymerization. Nuclear magnetic resonance and Fourier transform infrared spectroscopy were used to characterize the synthesis of the polysiloxanes. The rate of polymerization was found to increase as temperature, intensity, sol–gel precursor concentration, and exposure time were increased.     

Synthesis of fluorinated/methacrylated epoxy based oligomers and investigation of its performance in the UV curable hybrid coatings

Organic–inorganic hybrid coatings based on fluorinated/methacrylated soybean oil and bisphenol A/F epoxy methacrylate were obtained by combining photopolymerization and sol–gel process. Hard and transparent hybrid coatings were prepared on polycarbonate panels and their physical and mechanical properties such as gel content, hardness, adhesion, gloss, contact angle as well as tensile strength were measured. Results from the mechanical measurements showed that the properties of hybrid coatings improved with the increase in fluorine and sol–gel precursor contents. Thermo gravimetric analysis results demonstrated that fluorine and silica incorporations significantly enhanced the thermal oxidative stability of the hybrid coating materials. The surface morphology was also characterized by scanning electron microscopy (SEM). SEM studies indicated that inorganic particles were dispersed homogenously throughout the organic matrix.     

High performance polyaniline containing coating system for wet surfaces

Application of paint coatings on wet surfaces is rather difficult due to poor adhesion of coatings. For painting of wet surfaces, moisture curable coating systems based on epoxy resin and ketimine are found to be useful. Hence a study has been made on the corrosion protection ability of coating on wet surfaces using epoxy resin, ketimine and polyaniline. Paints with 20–30% PVC were prepared and applied over the wet steel surface and the corrosion protection performance of the coating was found out by salt spray and electrochemical impedance spectroscopic techniques. Coating with 20% PVC is found to offer very high protection since the impedance values are remained at greater than 10⁹ Ω cm² after immersion and salt spray tests.     

固化剂对环氧玻璃鳞片涂层性能的影响

以双酚A环氧树脂(E20)为主要成膜物,层片状玻璃鳞片和云母氧化铁为主要填料,辅助以铝粉、氧化铁红颜料,以及各种助剂和溶剂,再分别加入固化剂脂肪族胺加成物、聚酰胺TY-650,制得高固体分厚浆型环氧玻璃鳞片涂料。通过常规的力学性能(涂层的硬度、耐冲击性、柔韧性、附着力等)和耐腐蚀性测试,对比了不同固化剂对环氧玻璃鳞片涂层性能的影响。研究结果表明,脂肪族胺加成物与环氧树脂交联固化的玻璃鳞片涂层的硬度、附着力以及交流阻抗值都较高,具有良好的综合性能,加入铝粉对基体可起到阴极保护作用。     

Observations on chromate conversion coatings from a sol–gel perspective

Chromate conversion coatings (CCCs) have been applied to aluminum substrates for many years to improve corrosion resistance and paint adhesion. In recent years the so-called sol–gel chemistry based coating systems have been examined as possible replacements for CCCs on aluminum. A mechanism is proposed for the formation of CCC on aluminum that is consistent with sol–gel chemistry principles. The conclusions illustrate important considerations for developing non-CCCs for aluminum.     

Preparation and characterization of sol–gel derived UV-curable organo-silica–titania hybrid coatings

In this work, UV-curable organic–inorganic hybrid coatings based on cycloaliphatic epoxyacrylate were prepared by sol–gel technique. Acid catalyzed solutions of tetraethylorthosilane (TEOS) containing Ti:acac complex were used as an inorganic precursors. UV-curable, transparent hybrid coating materials were applied on plexiglass substrates and their coating performance was investigated by the analyses of various tests such as hardness, gloss, cross-cut adhesion tests, stress–strain test and optical transmission. The mechanical measurements showed that, the tensile properties of coatings underwent an abrupt change from a brittle to a tough material when the inorganic part was incorporated into the cycloaliphatic epoxy acrylate based organic network. UV–vis transmission spectroscopy results indicated that the hybrid materials with high titanium content have good transparences. The thermal behaviour of the coatings was also evaluated. It is observed that the thermal stability of the hybrids is enhanced with incorporation of sol–gel precursor.     

Effects of carbon nanotube content on adhesion strength and wear and corrosion resistance of epoxy composite coatings on AA2024-T3

The effects of multiwalled carbon nanotube (MWCNT) content on the adhesion strength and wear and corrosion resistance of the epoxy composite coatings prepared on aluminum alloy (AA) 2024-T3 substrates were evaluated using atomic force microscopy (AFM), blister test, ball-on-disk micro-tribological test and electrochemical impedance spectroscopy (EIS). The adhesion strength of the epoxy composite coatings improved with increasing MWCNT content. Increased MWCNT content also decreased the friction coefficient and increased the wear resistance of the epoxy composite coatings due to improved solid lubricating and rolling effects of the MWCNTs and the improved load bearing capacity of the composite coatings. Finally, EIS indicated that increased MWCNT content increased the coating pore resistance due to a decreased porosity density, which resulted in an increase in the total impedance of the coated samples.     

Passivation of metal alloys using sol–gel-derived materials — a review

The sol–gel method is being investigated as an environmentally compliant alternative for chromate-based conversion coatings currently in use. An overview of recent advances in the use of sol–gel derived coatings for improved corrosion resistance of aluminum and steel metal surfaces is given.     

Synthesis and performance evaluation of environmentally compliant epoxysilane coatings for aluminum alloy

Organosilane-based waterborne coatings for corrosion protection of aluminum alloy have been developed by sol–gel process. The coating solutions were prepared by hydrolysis and condensation of methyltrimethoxysilane (MTMS) and 3-glycidoxypropyltrimethoxysilane (GPTMS) in the presence of acid catalyst and amino functional organosilanes namely 3-aminopropyltrimethoxysialne (1N), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (2N) as hardeners. Coating materials were characterized using FT-IR, atomic force microscopy (AFM), UV–visible spectroscopy, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The optimum concentration of GPTMS to hardeners (1N and 2N) and the effect of MTMS:GPTMS molar ratios on corrosion resistance of coatings were studied. Corrosion resistance and porosity in coatings were measured by potentiodynamic polarization studies and electrochemical impedance analysis. Furthermore, hydrophobicity of the coatings was evaluated using contact angle measurements. Bend test, impact resistance test and pencil hardness test were carried out to evaluate the hardness and adhesion behavior of coating.

Results show that the coatings are continuous, defect free and well adherent to the substrate. Structural studies confirm the nanometric level of interaction among the coating components. None of the coating materials show the glass transition temperature in the temperature range of 30–700 °C. Coating materials are thermally stable up to 390 °C. EIS and potentiodynamic polarization studies suggest that the optimum concentration of GPTMS:NH are 1:1 and 3:2 (molar ratio) for 1N and 2N harden coatings, respectively. Improvement in corrosion resistance is observed with increasing GPTMS concentration in coatings. The average porosity of coatings is found to be 7.18% and 10.98% for 1N and 2N harden coatings, respectively. Water contact angle of these coatings are found in the range of 59–78 °C.     

Hybrid coatings from novel silane-modified glycidyl carbamate resins and amine crosslinkers

Organic–inorganic hybrid coatings were prepared using silane-modified glycidyl carbamate resins and different amine crosslinkers via the sol–gel process. Two different silane-modified glycidyl carbamate resins with 33% and 20% silane modification were prepared. The synthesized resins were crosslinked with amine crosslinkers such as Amicure PACM, Ancamide 805, Ancamide 2050, Ancamide 2353, Epicure 3164, Jeffamine D-400, etc., at different epoxy to amine equivalent ratios. The formulated hybrid coatings were cured at laboratory temperature and humidity for more than 20 days and subjected to different tests. The hybrid coatings were analyzed using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) during network maturation. Post-cured coatings were also analyzed to understand the effect of structural variables on the coatings thermal properties. Mechanical testing of the post-cured coatings such as König pendulum hardness, crosshatch adhesion and impact resistance were also evaluated. Solvent resistance of the coatings was evaluated by of testing the methyl ethyl ketone (MEK) double rub resistance. Atomic force microscopy (AFM) was used to characterize the surface topography of the hybrid coatings. Finally, structure–property correlations were given based on the observed results.     

Preparation of rough anatase films and the evaluation of their photocatalytic efficiencies

Sol–gel derived rough anatase films without controlled particle sizes were prepared by surfactant templating. The coating sol–gel was obtained by hydrolysis of Ti(OC₃H₇)₄ in ethanol/HNO₃ solution. The gel films, prepared by dipping glass substrates in surfactant solutions, were dried after immersion under an atmospheric pressure. The rough films of TiO₂ anatase were obtained after calcining at 500 °C. The resultant films were transparent, semitransparent or opaque and 136–402 nm thick. It was found that the TiO₂ films prepared from the sol–gel with surfactant showed a granular nanostructure, and they were composed of regular particles, for example; between 50 and 70 nm. The roughness of the films was found to depend on the surfactant concentration in the sol–gel solution and can show a roughness between 0.82 and near of 17 nm. The photocatalytic activity of the films for the degradation and mineralization of phenol, an industrial pollutant, in water and under 365 nm irradiation was improved by the surfactant modification. Kinetic analysis of degradation and mineralization of phenol in water were employed to evaluate the different TiO₂ films under the same experimental conditions. The global photonic efficiency for degradation and mineralization of phenol ξ_g, was calculated to facilitate comparison with a TiO₂ standard photocatalyst named Degussa P-25.     

Polymeric sol–gel coatings as protective layers of aluminium alloys

Sol–gel route is an emerging technology to synthesize coatings of a wide variety of properties taylored. In this work three low temperature cured coatings has been studied to evaluate their protective properties in order to be used as protective barrier coatings for aluminium alloys with potential architectural and automotive applications. These three coatings are novel modified silane nanocomposites coatings obtained mixing two sols separately prepared: a pre-hydrolysed 3-glycidyloxypropyl trimethoxysilane (GPTS) with acidic catalyst and another obtained from tetraethylorthosilicate/methyltriethoxysilane (TEOS/MTES). Particulated coatings were obtained by addition of 25 wt.% particles of Aerosil 300 and Aerosil R972, respectively. The protective properties of the coatings were evaluated by electrochemical impedance spectroscopy (EIS) which showed notably differences among them not only from the protective viewpoint but the hydrophobic nature of the coatings and the controlling corrosion mechanism in each case.