Active metal-based corrosion protective coating systems for aircraft requiring no-chromate pretreatment

There has been much R&D effort expended to develop pretreatments and coatings that allow the replacement of toxic, carcinogenic, mutagenic, environmentally hazardous chromates used as pretreatments and pigments in aircraft coating systems. There have been many claims for chromate replacement in primer and pretreatment systems for aircraft, but no systems presently are in use that can function and meet specifications without some form of chromate used in the pretreatment and/or primer. The Mg-rich primer technology developed at North Dakota State University and now in final commercial development at AKZO Nobel Aerospace Coatings shows that finally aerospace Al alloys can be protected against corrosion. With simple cleaning only or a non-chromate pretreatment, the Mg-rich primer (MgRP) + aerospace topcoat provides an aircraft protection system that give corrosion protection that equals or exceeds any system using chromate in any form. About 18 peer reviewed papers have been published and at least twice that many presentations at technical meetings describing this new aircraft primer technology. There are an extensive number of samples in outdoor exposure, and in exposure on small parts of aircraft like port-hole covers and doors, and the coating system has been in accelerated exposure cabinets of all sorts. In the first versions of the magnesium primer premature blistering was noted during immersion or B117 continuous salt spray testing which may be due to hydrogen generation from water contact at a particle. Efforts to control the level of activity of the magnesium have been successfully accomplished since the testing reported in this paper which controls this phenomenon. Current formulations meet and exceed the ASTM B117 test results of full chromate primer systems. Open circuit potential (OCP) measurements indicate an extended period of cathodic protection of the Al aircraft alloys such as AA 2024 T-3 and AA 7075 T-6. After this stage of protection, a combination of Mg oxide, hydroxide and carbonate compounds seem to give protection to the system, as we have seen corrosion protection given to samples for greater than 10,000 h of cyclic exposure for Mg-rich primers with good aerospace topcoats. Preliminary data are presented for other Mg alloys as pigments in metal-rich coating systems. All data indicates that the Mg-rich (or Mg-alloy pigment-rich) primer + aircraft topcoat system gives excellent corrosion protection by mechanisms entirely different from the modes of protection for aircraft alloys given by the toxic, carcinogenic chromate compounds now in use in all corrosion protection systems for aircraft. In most cases thus far examined, the protection, especially in cyclic exposure, exceeds the present chromate-based systems.     

Hybrid nanocomposite coating by sol–gel method: a review

The development of environmentally friendly process for pretreatments of metallic substrates is a field of growing research due to the ban against chromates used as protective pretreatments. Among the possible candidates for environmentally friendly pretreatments of aluminum alloys are the silica-based sol–gel coatings. Such coatings are able to form an Si–O–Al conversion layer providing a stable alumina/sol–gel film interface, which inhibits the onset of corrosion. Sol–gel technology offers a wide range of chemical mechanisms and exhibits high potential substitutes for the environmentally unfriendly chromate metal-surface pretreatment. Sol–gel derived organo-silicate hybrid coatings, preloaded with organic corrosion inhibitors, have been developed to provide active corrosion protection when integrity of the coating is compromised. The incorporation of organic corrosion inhibitors into hybrid coatings has been achieved as a result of physical entrapment of the inhibitor within the coating material at the stage of film formation and cross-linking. Sol–gel derived coatings, especially the hybrid films, provide a dense barrier against electrolyte uptake, and offer a wide range of applications as corrosion protective, hydrophilic coatings, hydrophobic anti-reflective coatings, migration barriers against liquid and volatile compounds, antibacterial modification of textiles and water-repellent antistatic textiles. In this paper, the novel applications of the sol–gel derived coatings are presented and discussed.     

Properties of ketimine/acetoacetate coated aluminum substrates

Based on ketimine/acetoacetate coating technology, a new two-component high solids primer for aerospace use has been developed. The objective was to formulate a chromate-free primer that may be applied to all relevant aluminum surfaces, particularly after chromate-free pretreatment. During development, interesting indications of good adhesion and good corrosion resistance were found. For confirmation and in order to optimize the primer, research was focused on the interfacial performance of the coatings on typical aerospace substrates. In this paper, therefore, the nature of the substrates, including their pretreatments, is discussed with initial emphasis on the nitric acid pickling pretreatment, used in place of chromate pretreatments with their desirable properties. Although aging in relevant electrolytes of such pretreated aluminum leads to an increase of the thin oxide layer by further hydration normally influencing negatively interfacial performances, cross cut adhesion values of the primer, or the primer/topcoat, before and after aging in several electrolytes, were good on clad as well as on non-clad material. This was confirmed by microscopic morphology assessment during similar aging processes of the coating/substrate systems. The hydration of the nitric acid pickled layer was not found in the presence of primer, with or without topcoat. Using electron energy loss spectroscopy, indications of a distinct chemical bond between the primer and the nitric acid pickled aluminum were revealed. Electrochemical impedance measurements, determining film resistances of the various coated panels, also showed good responses when the primer was pigmented with a selected chromate-free inhibitor. Finally, in line with the previous indications and due to the special interfacial performance, in the presence of chromate-free pretreated substrates, filiform corrosion resistance with chromate alternative pigmentation approaches that of chromated primers.     

Polyurethane/Polysiloxane Ceramer Coatings: Evaluation of Corrosion Protection

A series of polyurea and polyurethane ceramer coatings were formulated using hexamethylene diisocyanate (HDI) isocyanurate, alkoxysilane‐functionalized HDI isocyanurate, tetraethyl orthosilicate (TEOS) oligomers and cycloaliphatic polyesters. The coatings were prepared as a function of alkoxysilane‐functionalized HDI isocyanurate and TEOS oligomers concentration. Also, the effect of acid catalyst was investigated. The corrosion resistance of polyurea or polyurethane ceramer coating systems were evaluated using a prohesion chamber on aluminium alloy 2024‐T3 substrate. The polyurethane ceramer coatings were compared with the chromate pretreatment and the epoxy‐polyamide primer containing the chromate pigment. In addition to prohesion, the interface between the coating and substrate was characterized using X‐ray photoelectron spectroscopy (XPS). The prohesion data showed that the corrosion was inhibited by the TEOS oligomers. However, high concentrations of TEOS oligomers and acid catalyst produced blistering in the polyurea/polysiloxane ceramer coatings. The prohesion data also showed that the corrosion protection of ceramer coatings performed as well as the chromate pretreatment and competitively with the epoxy primer. From the XPS and prohesion data, a self assembling silicon oxide layer at the metal‐coating interface was proposed.     

Novel,one-step,chromate-free coatings containing anticorrosion pigments for metals—An overview and mechanistic study

The concept of superprimers, i.e., primers for metals with the conversion coating built in, has proven to be feasible. Such primers do not require a chromate (or other) conversion treatment of the metal and can be applied on any bare metal. The VOC content in the primer is kept low by using water-dispersed organic resins. Because of the high concentration of organofunctional silanes contained in the superprimer, its adhesion, both to the substrate and to overcoats, is excellent. The corrosion resistance of the primer can further be improved by adding corrosion-inhibiting pigments such as micronized zinc phosphate into the formulation. The corrosion protection performance of these coatings has been evaluated using performance tests and electrochemical methods. The primers have also been characterized with a variety of surface analytical methods. It will be shown that 2000 h of salt spray resistance has been obtained with the primers both on AA2024-T3 and HDG steel. This study will mainly present an overview of the chromate-free primers studied in our laboratory and will attempt to explain the mechanism by which one of the coatings, the epoxy–acrylate-based primer deposited onto aluminum, protects the metal from corrosion.     

Characterization of active pigments in damage of organic coatings on steel by means of electrochemical impedance spectroscopy

Active anticorrosive pigments are solid additives for primers which can give further protection for areas with coating damage in addition to their barrier effect. These pigments are expected to prevent corrosion of metal substrate in coating damage by build-up of permanently passive conditions at the metal surface (electrochemical protection) and/or by build-up of solid compounds which plug the coating damage (chemical protection). Electrochemical Impedance Spectroscopy (EIS) was applied to characterize the corrosion protection behaviour of alkyd primers containing different pigments. Impedance spectra were recorded in the frequency range 50 mHz f 50 kHz at the open-circuit potential as a function of the type of pigment and the exposure time in different corrosive media. In general, two different parts can be distinguished in the impedance diagrams. The higher frequency part is related to the insulating properties of the primer and the lower frequency part can be attributed to electrochemical processes taking place within the coating defects. The parameters derived from EIS results show that the low frequency data can be used for characterization of the protective properties of anticorrosive pigments in the presence of defects in organic coatings.     

Challenges of chromate inhibitor pigments replacement in organic coatings

General considerations concerning pigment grade corrosion inhibitors are presented and new characteristic functional parameters proposed. The chemistry, contemporarily practiced for corrosion inhibitor pigment synthesis, as well as known mechanistic considerations relevant to the corrosion inhibitor species available in pigment grades, are reviewed. Inherent limits of chemistry are outlined regarding the feasibility of developing equally effective and versatile non-toxic alternatives for chromates.

Fundamental aspects of corrosion inhibitor pigment behavior are discussed in the context of organic coatings degradation mechanisms. Disclosed experimental data demonstrate that correlation exists between solubility of corrosion inhibitor pigments, leaching from, and osmotic blistering of organic coatings. A mathematical expression is proposed and empirically proven to adequately describe the leaching rate of corrosion inhibitor pigments from organic coatings.

The barrier function of some high performance organic coatings, such as aircraft or coil, is negligible and requires the contribution of an effective corrosion inhibitor pigment, which, typically, is strontium chromate. In this context, the feasibility of replacing chromate inhibitor pigments is assessed and the “gap” observable between the inhibitor performance of chromates and traditional non-chromate pigments is noted.

Experimental data are displayed regarding the corrosion inhibitor performance of a novel, organic–inorganic, hybrid type corrosion inhibitor pigment in typical aircraft primer application on aluminum and plated steel. The presented data demonstrate the feasibility of chromate replacement in this specific case.     

Corrosion protection of galvanized iron by polyaniline containing wash primer coating

Wash primer treatment of galvanized iron (GI) structure is widely used before painting in order to improve adhesion. Traditional wash primer contains zinc tetroxy chromate. Due to hazardous nature of chromate, alternate compounds for chromate replacements have been identified. In recent years polyaniline containing coating has been found to protect GI. In this study, a wash primer based on polyaniline has been formulated and its corrosion protection ability of GI has been compared with that of traditional chromate based wash primer by salt spray and EIS test. It has been found that the polyaniline based wash primer is able to protect GI and its corrosion protection performance is similar to chromate based wash primer coating.     

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.     

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.     

Mg-rich coatings: A new paradigm for Cr-free corrosion protection of Al aerospace alloys

Environmentally acceptable alternative coatings to chromate pigments and pretreatments for the corrosion control of Al alloy 2024 T-3, commonly used in aircraft, were designed, formulated, and tested as primer coatings to provide protection using particulate Mg-rich pigmentation. The system was designed by analogy to pigmented Zn-rich primer coatings used for the protection of steel. In the current study, four coating polymer systems were examined as possible candidates as polymer matrices for Mg-rich cathodic protect coatings. Mg-rich primers were formulated with ∼50-micron average particle size magnesium powder, near to the critical pigment volume concentration (CPVC) for this system. Top-coated scribed coatings systems have been subjected to Prohesion^™ exposure in dilute Harrison’s solution for up to 5000 hr. These coatings are the first nonchromated coatings to satisfy 3000 hr of such exposure and remain shiny and undamaged in the scribe area, only showing damage at about 4800 hr. The corrosion byproducts generated in the scribe areas during Prohesion exposure were examined by energy dispersive X-ray analysis (EDXA), and the local pH of the coating determined by the nature of the salt formed as a function of exposure conditions and time, did not cause Al corrosion. Presented at the 81 st Annual Meeting of the Federation of Societies for Coatings Technology, November 12–14, 2003, in Philadelphia, PA.     

石化防腐涂装工程表面预处理要求评述

石化设备与钢结构防腐涂装前须进行表面处理,表面处理对涂层使用寿命至关重要。探讨了涂层下金属腐蚀、涂层附着力、表面预处理与各类底漆相互关系。认为采用锈面底漆与多功能环氧涂料是较好办法。     

The mode of action of chromate inhibitor in epoxy primer on galvanized steel

Investigations of the mechanism of the protective action of strontium chromate pigment in an epoxy primer were carried out with electrochemical impedance spectroscopy (EIS), atomic absorption spectroscopy (AAS), scanning reference electrode techniques (SRET) and water uptake measurements. Epoxy primers applied to galvanized steel were studied in a corrosion environment which models the atmospheric precipitation of European countries. Corrosion and electrochemical properties of samples of bare galvanized steel and coated galvanized steel were investigated. It was established that the protective function of the chromate in the primer is primarily due to a cathodic/mixed inhibition of the surface of galvanized steel in defect areas of the polymer coating. It is suggested that the process of leaching of chromate ions from epoxy primer into the environment takes place because the decrease in pH at anodic defect sites causes the destruction of the primer film and accelerates the dissolution of the chromate pigment.     

The role of hexafluorozirconate in the formation of chromate conversion coatings on aluminum alloys

Aluminum based surfaces are routinely coated with a chromate based layer that provides unparalleled corrosion protection. Widely used conversion coating treatment formulations contain hexafluorozirconate as a major constituent besides chromate, ferricyanide, fluoride, and fluoborate. The function of hexafluorozirconate is the subject of this study as its function is still largely unknown. Hydrophobicity, surface morphology, and the chemistry of the surface, resulting from treatment with hexafluorozirconate, were studied using contact angle measurements, scanning electron microscopy, and energy dispersive spectroscopy, respectively. X-ray photoelectron spectroscopy was extensively utilized to determine the chemistry of the surface resulting from the hexafluorozirconate pretreatment. Our results indicate that fluoride ion containing hexafluorozirconate complex does not attack the oxide film in a manner that uncomplexed simple fluoride ion does. Hexafluorozirconate is involved in the formation of an Al-Zr-O-F based hydrated layer that increases the hydrophilicity of the surface, activates the surface, and lowers the corrosion resistance. These factors enhance the interaction of chromate with the alloy surface to result in the formation of a uniform conversion coating. Based on these results, a new model has been proposed for the formation of chromate conversion coatings.     

Corrosion protection behavior of AZ31 magnesium alloy with cathodic electrophoretic coating pretreated by silane

As an alternative process to phosphate and chromate conversion coatings, silane pretreatment was used to improve the performance of cathodic electrophoretic coating (E-coat) on AZ31 Mg alloy in this study. The galvanic corrosion behavior of AZ31 Mg alloy with E-coat coupled with Q235 steel was investigated. Compared to bare Mg alloy and Mg alloy with conventional painting, the corrosion properties of the AZ31 Mg alloy pretreated with silane and subsequently E-coated were studied during salt solution immersion and salt spray testing. The surface morphologies of the Mg alloy were examined in detail after immersion in NaCl solution for different times using digital photography and scanning electron microscopy (SEM). The corrosion current density of the specimens was characterized by DC polarization tests. It was found that silane pretreatment of AZ31 Mg alloy followed by subsequent E-coat led to much better corrosion protection than that without silane treatment. The silane pretreatment and E-coat delayed the galvanic corrosion of Mg alloy coupled with 235 steel bolts.     

Effect of bath concentration and curing time on the structure of non-functional thin organosilane layers on aluminium

The corrosion resistance of aluminium alloys can be improved by different surface treatments such as painting. A pre-treatment based on chromate is the current method used to increase the corrosion resistance and the adhesion of the organic layer. Silane films seem to be an interesting alternative system to replace the toxic chromates. In this paper, the characterisation of bis-1,2-(triethoxysilyl)ethane (BTSE) thin layers has been evaluated by coupling optical techniques like spectroscopic ellipsometry (SE) and infra-red spectroscopic ellipsometry (IRSE) along with electrochemical methods (electrochemical impedance spectroscopy (EIS)). This approach has been chosen to have a better understanding of the protection provided by these organosilane thin films. It will be demonstrated that the BTSE bath concentration modifies the thickness of the layers and that the curing of this thin film can also improve the barrier properties by forming a denser layer.     

[V10O28]6-柱撑纳米水滑石在AZ31镁合金有机防腐涂层中的应用

研制了一种以钒酸盐阴离子([V10O28]6-)柱撑纳米水滑石防腐颜料替代铬酸盐,用于AZ31镁合金腐蚀防护的有机涂层.研究了水滑石在不同浓度的NaCl溶液里的吸附和离子交换性能,以及钒酸盐缓蚀剂的极化曲线:考察了该水滑石防腐颜料的添加比例对镁合金环氧防腐涂层性能的影响,并通过电化学交流阻抗(EIS)测试技术对各试样进行了性能检测.结果表明,添加了20%(质量分数)水滑石的环氧涂层对镁合金具有较好的防腐作用.     

Corrosion inhibition of aluminum by organic coatings formulated with calcium exchange silica pigment

One of the first commercial ion-exchange anticorrosive pigments to be developed was Shieldex^® (Si/Ca). Its proposed corrosion protection mechanism, based on the retention of aggressive cations and the subsequent release of calcium cations, has created certain controversy. A number of studies have focused on the anticorrosive behavior of this pigment on carbon steel and galvanized steel to replace chromates (Cr⁶⁺) as inhibitor pigment, but none has considered its performance on aluminum or aluminum alloys. In this research, alkyd coatings have been formulated with Si/Ca pigment at different concentrations and applied on aluminum 1050 (Al 99.5%) specimens. These specimens have then been subjected to accelerated tests (condensing humidity, salt spray, and Kesternich) and natural weathering in atmospheres of different aggressivity. Corrosion performance has been also evaluated in the laboratory by electrochemical impedance spectroscopy. The study has also considered an organic coating with zinc chromate anticorrosive pigment for comparative purposes. The results obtained with organic coatings formulated with Si/Ca pigments confirm that they provide corrosion protection of the underlying aluminum substrate, even improving the behavior of the reference zinc chromate in some environmental conditions.     

Corrosion protection properties of silane pre-treated powder coated galvanized steel

Silane based products are becoming an interesting material for pre-treatment deposition, because, for the environmental compatibility, they can be used as substitutes of traditional pre-treatments like chromates. Silanes have been studied as new pre-treatments before organic coating deposition for many different metals, including aluminium, copper and zinc.In this work, some results concerning the properties of water-based silane pre-treatments on galvanized steel will be presented.Galvanized sheets obtained by continuous hot dip process were considered. A silane based bath containing a mixture of three different silanes were used for the pre-treatment deposition (Glycidoxypropiltrimethoxysilane, Tetraethoxysilane and Methyltriethoxysilane).The obtained pre-treatments were characterized by SEM observations, FT-IR and ToF-Sims analysis. The corrosion protection properties of the pre-treated galvanized samples were studied using industrial accelerated tests (like salt spray exposure) and electrochemical measurements (polarization curves and electrochemical impedance spectroscopy (EIS) measurements), as a function of the different curing conditions. The pre-treated galvanized sheets were further coated with an epoxy-polyester powder coating, in order to verify the adhesion promotion properties and the corrosion protection performances of the complete protective system.The coated samples were characterized by EIS measurements with artificial defect in order to study the interfacial stability (adhesion) in wet conditions and monitor the coating delamination.The electrochemical data were compared with adhesion measurements obtained by cathodic delamination tests. The electrochemical tests showed that the silane layer acts not only as a coupling agent between the inorganic substrate and the organic coating, but it also ensures a good barrier effect against water and oxygen.     

High performance reaction-induced quasi-ceramic silicone conversion coating for corrosion protection of aluminium alloys

Regulations posed by the Environmental Protection Agency on the use of chromate conversion coatings have triggered the need to find alternative materials for the corrosion protection of aluminium and its alloys. A simple four-step process of creating a quasi-ceramic coating has been developed. The coating, which is made of environmentally safe chemicals, should be easily and safely manufactured for bulk production. Here, we describe the synthesis, characterization and evaluation of a silicone conversion coating for aluminium metal and its alloys. The spectroscopic techniques utilised in this study have shown the mode of the bonding mechanism between the metal and the coating. Thermal analysis of the material was conducted to evaluate its stability, while nano-mechanical properties were determined and correlated with the surface morphology of the coating. Results obtained from FTIR and XPS spectroscopic techniques suggested that the coating adhered to the metal substrates through active surface functionalities, and thermal analysis showed that the coatings contained volatile solvents including water that evaporated at lower temperatures. Nano-mechanical tests suggested that the coating had elastic properties. Accelerated corrosion and immersion tests were also performed on coated and uncoated aluminium alloys. Coated and uncoated aluminium alloys were also exposed to soil containing sulphate-reducing bacteria. Coated coupons showed excellent corrosion protection and antifouling characteristics indicating that the coatings were impervious and of high integrity.