Improving corrosion resistance of aluminium metal matrix composites using cerium sealed electroless Ni–P coatings

Abstract

A conversion coating treatment using cerium salts was developed for the surface sealing of electroless nickel–phosphorus (Ni–P) coatings on carbon fibre reinforced aluminium (Cf/Al) composites. The corrosion resistances of uncoated and coated materials (i.e. the Ni–P coating, the Ce conversion coating and Ce sealed Ni–P coatings) were evaluated in 3·5 wt-%NaCl solution using potentiodynamic polarisation and electrochemical impedance spectroscopy. Ce sealed Ni–P coating showed the highest corrosion resistance and clearly improved the overall corrosion resistance of Cf/Al composites. Thus, the Ce sealed Ni–P coating had no obvious microcracks that were generally evident in the more conventional Ce conversion coatings. This is presumed to occur because the electroless nickel surface is relatively homogeneous, compared with the Cf/Al composite surface on which different local coating thicknesses would encourage increased microcrack formation. X-ray photoelectron spectroscopy analysis showed that the Ce conversion coating mainly contained both Ce³⁺ and Ce⁴⁺ species; however, Ce⁴⁺ species were the dominant oxidation state on Ce sealed Ni–P coatings.     

The characterization and corrosion resistance of cerium chemical conversion coatings for 304 stainless steel

A golden yellow-colored cerium conversion coating was obtained on 304 stainless steel surface by immersing the steel into a solution containing cerium (III), KMnO₄ and sulfuric acid. The corrosion resistance of the coatings was evaluated by electrochemical methods, potentiodynamic polarization experiments and electrochemical impedance spectrum. The experimental results indicated that the corrosion resistance for the conversion coated 304SS in 3.5% NaCl solution increased markedly. The corrosion potential of the treated steel increased to a more noble level, the pitting corrosion potential increased also, the passive potential range was enlarged markedly and the passive current density decreased about one order compared to that of the untreated steel. The cathodic and anodic reaction were both inhibited to some extent. The chemical state of the elements in the coatings was investigated by XPS. The cerium element was in the form of tetravalent state. And AES depth profile analysis suggested that the thickness of the conversion coatings was less than 66 nm. The mechanisms of coatings formation and corrosion resistance are discussed.     

Study on corrosion behaviour of nanocrystalline and amorphous Co–P electrodeposits

Abstract

In this study, corrosion properties of nanocrystalline and amorphous Co–P coatings prepared using dc electrodeposition were investigated. The morphology of amorphous coatings was smoother and brighter than nanocrystalline coatings with 'cauliflower' morphology. Tafel polarisation tests of the coatings in 0·1M H₂SO₄ solution revealed that the amorphous coating had better corrosion resistance than the nanocrystalline one. Corrosion resistance of both coatings decreased after annealing. On the nanocrystalline coating, corrosion attacks were localised around the nodules on the surface while a more uniform type of attack was observed on amorphous coatings. Neither nanocrystalline nor amorphous coatings showed passivation in 0·1M H₂SO₄ solution, but both of them showed an active–passive behaviour in 10%NaOH solution due to the formation of Co(OH)₂ as fine hexagonal shape products which acted as a passive layer. The passive current density of the amorphous coating was higher than that of the nanocrystalline one, but it was decreased markedly by annealing. However, annealing had no significant effect on the passivation behaviour of the nanocrystalline coating.     

Electrochemical corrosion behaviour of microcrystalline aluminium in acidic solutions

The electrochemical corrosion behaviour of microcrystalline pure aluminium coating, fabricated by a magnetron sputtering technique, has been investigated in both 0.5 mol/l NaCl and 0.5 mol/l Na₂SO₄ acidic (pH = 2) aqueous solutions. The corrosion resistance of the microcrystalline Al coating has deteriorated more compared with that of the cast pure Al in Na₂SO₄ acidic solution. However, its oxide film has a higher pitting resistance in the NaCl acidic solution. Chloride ions play a big role in the formation of the oxide film on the microcrystalline Al coating. The higher pitting resistance was attributed to the more acidic isoelectric point which the oxide film achieved.     

几种添加剂作用的微弧氧化膜表面结构及防腐性能

为定性比较添加剂对涂层防腐性能的作用,通过恒压微弧氧化(MAO)方法在AZ31B镁合金表面制备氧化陶瓷膜,采用扫描电子显微技术(SEM)、中性盐雾试验(NSS)等手段,考察了KOH及添加剂Na_2B_4O_7、C_6H_5Na_3O_7和EDTA-2Na浓度(质量浓度)对MAO膜表面形貌、防腐性能、粗糙度和厚度的影响。结果表明:单一组分Na_2SiO_3电解液因较高起弧电压而未能在260 V恒压条件下获得具有"火山口"形貌特征的MAO膜,其防腐性能较差。适量KOH因较低微弧等离子体诱发电压和OH-较快的放电作用,提高了涂层的防腐性能。在优化的Na_2SiO_3-KOH体系中引入10~15 g/L Na_2B_4O_7,因其特殊的形成过程及其"火山喷射状"的微结构,且获得的MAO膜具有自封孔结构,提高了其对镁合金的点腐蚀防护性能。C_6H_5Na_3O_7和EDTA-2Na具有抑弧效应,获得的MAO膜表面微孔分布均匀,但降低了MAO膜的厚度、粗糙度以及防腐性能。     

Effect of heat treatment on pitting corrosion resistance of 6061 Al/SiC<Subscript>P</Subscript> composite coated by the cerium oxide film in 3.5 N NaCl solution

One of the main drawbacks of 6061 Al/SiC_P composite is its poor pitting corrosion resistance in the aggressive environment containing chloride ions, such as seawater, for example. The present article deals with the investigations of effects of aging on the corrosion behavior of 6061 Al/SiC_P composite and of the heat treatment on the pitting corrosion resistance of 6061 Al/SiC_P composite coated by cerium oxide prepared by chemical bath technique. Potentiodynamic polarization test was used to study the corrosion behavior of cerium oxide coatings in 3.5N NaCl solution. The microstructure of cerium oxide was examined by scanning electron microscopy (SEM) and the formed phases were identified by X-ray diffraction (XRD). The pitting corrosion resistance of the cerium oxide coating was found to be improved after heat treatment at 300°C for 30 min.     

Effect of SiO2:Na2O molar ratio of sodium silicate on the corrosion resistance of silicate conversion coatings

Passivation treatment by sodium silicate solution is considered as an alternative to chromium chemical conversion treatment to improve the corrosion resistance of hot-dip galvanized (HDG) steels. In this paper, a transparent silicate coating was formed on the surface of HDG steel by immersing in sodium silicate solution with SiO₂:Na₂O molar ratio in the range from 1.00 to 4.00. The parameter about the SiO₂:Na₂O molar ratio of silicate solution has been discussed using corrosion resistance and surface morphology. Tafel polarization, electrochemical impedance spectroscopy (EIS) measurements and neutral salt spray (NSS) test show that silicate coatings increase the corrosion resistance of HDG steels. From the results obtained, it is deduced that the optimum SiO₂:Na₂O molar ratio is 3.50. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction analysis (XRD), and reflectance absorption infrared spectroscopy (RA-IR) show that there are no obvious differences of the chemical composition and structure in various silicate coatings. The silicate coatings mainly consist of zinc oxides/hydroxides, zinc silicate and SiO₂. However, atomic force microscopy (AFM) images reveal that the surface of silicate coatings with a molar ratio of 3.50 is more compact and uniform than other silicate coatings.     

黄铜在含磷酸二氢钠或硅酸钠的铝酸盐电解液中的等离子电解氧化行为和耐腐蚀性能（英文）

采用等离子电解氧化(PEO)技术对黄铜进行表面处理,研究其在铝酸盐电解液中分别加入NaH₂PO₄ (S1)和Na₂SiO₃(S2)添加剂对涂层形成和耐腐蚀性能的影响。在S1电解液中进行PEO处理的初始阶段,黄铜表面形成AlPO₄和Al₂O₃的混合涂层,导致快速产生等离子体火花放电现象并形成由Al₂O₃、CuO、Cu₂O和ZnO组成的黑色涂层。然而,在S2电解液中,等离子体火花放电行为延迟产生。由于产生较多的Cu₂O,S2涂层显示为深红棕色。Mott-Schottky测试表明,S1涂层为p型半导体;S2涂层具有n型和p型半导体可调性。动电位极化和电化学阻抗谱(EIS)测试表明,PEO处理能显著提高黄铜的耐腐蚀性,腐蚀防护效率可达91.50%,S1涂层电荷转移电阻最大可达59.95 kΩ·cm²。     

An Investigation into the Corrosion Behavior of MgO/ZrO<Subscript>2</Subscript> Nanocomposite Coatings Prepared by Plasma Electrolytic Oxidation on the AZ91 Magnesium Alloy

Plasma electrolytic oxidation (PEO) of AZ91 Mg alloys was performed in ZrO₂ nanoparticles containing Na₂SiO₃-based electrolytes. The phase composition and the microstructure of PEO coatings were analyzed by x-ray diffraction and scanning electron microscopy followed by energy dispersive spectroscopy. Pitting corrosion properties of the coatings were investigated using cyclic polarization and electrochemical impedance spectroscopy tests in a Ringer solution. The results showed the better pitting corrosion resistance of the composite coating, as compared to the oxide one, due to the thickened inner layer and the decrease in the surface defects of the composite coating. Also, the PEO process decreased the corrosion current density from 25.06 µA/cm² in the Mg alloy to 2.7 µA/cm² in the oxide coating and 0.47 µA/cm² in the composite coating.     

Improvement of corrosion resistance of AZ31 Mg alloy by anodizing with co-precipitation of cerium oxide

Anodizing of AZ31 Mg alloy in NaOH solution by co-precipitation of cerium oxide was investigated. The chemical composition and phase structure of the coating film were determined via optical microscopy, SEM and XRD. The corrosion properties of the anodic film were characterized by using potentiodynamic polarization curves in 17 mmol/L NaCl and 0.1 mol/L Na₂SO₄ solution at 298 K. The corrosion resistance of AZ31 magnesium alloy is significantly improved by adding cerium oxide to alkaline solution. In addition, the surface properties are enhanced and the film contains no crack.     

Self healing ability of silicate conversion coatings on hot dip galvanized steels

The self-healing ability of a coating is an important aspect for evaluating its corrosion resistance. Chromate conversion coatings show excellent anti-corrosion properties because of their compact microstructure and their strong self-healing ability. Silicate conversion coatings, which are potential replacement candidates for chromate conversion coatings, have good corrosion resistance, but their self-healing abilities have not been determined. In this paper, silicate conversion coatings are prepared by immersing hot dip galvanized steel sheets in sodium silicate solutions with SiO₂:Na₂O molar ratio of 1.00 and 3.50. The coatings are scratched with a blunt knife edge and corroded in a neutral salt spray chamber for certain lengths of time. The corrosion products in and near the scratched area are investigated by scanning electron microscopy and energy-dispersive spectroscopy. The self-healing ability of silicate conversion coatings is discussed. The results show that silicate conversion coatings have self-healing abilities under the experimental conditions. Higher SiO₂:Na₂O molar ratios lead to improved self-healing abilities. During the corrosion process, the silicate anions in the coating migrate to the scratched area, where a new conversion coating composed of Zn, O, and Si is formed. This delays corrosion in the scratched area.     

A room temperature cured sol–gel anticorrosion pre-treatment for Al 2024-T3 alloys

The inherent reactivity of the Al–Cu alloys is such that their use for structural, marine, and aerospace components and structures would not be possible without prior application of a corrosion protection system. Historically these corrosion protection systems have been based upon the use of chemicals containing Cr(VI) compounds. Organic–inorganic hybrid silane coatings are of increasing interest in industry due to their potential application for the replacement of current toxic hexavalent chromate based treatments. In the present study, a hybrid epoxy–silica–alumina coating with or without doped cerium nitrate has been prepared using a sol–gel method. The hybrid coatings were applied by a dip-technique to an Al–Cu alloy, Al 2024-T3, and subsequently cured at room temperature. The anticorrosion properties of the coatings within 3.5% NaCl were studied using electrochemical impedance spectroscopy (EIS), and conventional DC polarisation. An exfoliation test method involving immersion in a solution of 4 M NaCl, 0.5 M KNO₃ and 0.1 M HNO₃ was also used. The cerium nitrate doped sol–gel coating exhibited excellent anticorrosion properties providing an adherent protection film on the Al 2024-T3 substrate. The resistance to corrosion of the sol–gel coating was also evaluated by analysing the morphology of the coating before and after corrosion testing using scanning electron microscopy.     

Improving corrosion resistance of pure Al through ECAP

Abstract

Significant grain refinement and corrosion resistance improvement were achieved in industrial pure Al through equal channel angular pressing (ECAP). The effect of microstructure change on its corrosion resistance was investigated by optical/electron microscopy observation, constant immersion tests, polarisation tests and electrochemical impedance spectroscopy (EIS) in aqueous NaCl solution. The ultrafine grained (UFG) bulk pure Al (with grain sizes of 300–500 nm) has a higher pitting potential E_pit, a lower corrosion current density I_corr in polarisation tests and an increased polarisation resistance R_p from EIS plots, along with reduced corrosion damage in immersion tests, compared with the as cast material. It was found that the improved corrosion resistance resulted from the uniform distribution of fine Si containing impurities and the formation of a denser oxide film. The ECAPed samples with smaller Si containing impurities have lower microgalvanic currents and reduced susceptibilities of pitting corrosion, which is consistent with the classical ‘small cathode, large anode’ mechanism. The strain induced crystalline defects, for example, high angle grain boundaries and dislocations, appear to provide more nucleation sites for the formation of a denser and thicker oxide film, thus enhancing its corrosion resistance.     

Corrosion behavior of thermal-sprayed WC cermet coatings in SO4 2− environment

A series of the electrochemical and long-term corrosion tests was carried out in a 3.5 wt% Na2SO4 solution on thermal-sprayed WC-17Co and WC-10Co-4Cr cermet coatings in order to examine the effect of composition of binder materials on the corrosion behavior. The results reveal that the overall corrosion resistance of the WC-17Co coating is inferior to that of the WC–Co–Cr coatings due to the corrosion of binder materials which induce WC particles to fall off. CoO and WO3 oxide films form on the surface of WC-17Co coating in Na2SO4 solution electrochemical corrosion process, which will protect the coating in the process of corrosion. Cr2O3 oxide film formed on the WC-10Co-4Cr coating surface has a strong hindered role to corrosion. The corrosion mechanism of WC-17Co coating in Na2SO4 solution is entire corrosion of Co matrix, while it is film-hole corrosion mechanism for WC-10Co-4Cr coating.     

Electrochemical study on hot corrosion of Si-modified aluminide coated In-738LC in Na2SO4-20 wt.% NaCl melt at 750 °C

The corrosion performance of the slurry Si-modified aluminide coating on the nickel base superalloy In-738LC exposed to low temperature hot corrosion condition has been investigated in Na₂SO₄-20 wt.% NaCl melt at 750 °C by combined use of the anodic polarization and characterization techniques.The coated specimen showed a passive behavior up to −0.460 V vs. Ag/AgCl (0.1 mol fraction) reference electrode, followed by a rapid increase in anodic current due to localized attack in the higher potential region. In the passive region, the anodic dissolution of constituents of the coating occurred through the passive film, probably SiO₂, at slow rate of 20-30 μA/cm². The passive current for the Si-modified coating was two orders of magnitude smaller than that for bare In-738LC, which is known as Cr₂O₃ former in this melt. This indicates that the SiO₂ film is chemically more stable than Cr₂O₃ film under this condition. However, pitting-like corrosion commenced around −0.460 V and proceeded at the high rate of 100 mA/cm² in the higher potential region than +0.400 V. The corrosion products formed on the coating polarized in different anodic potentials were characterized by SEM, EDS and XRD. It was found from the characterization that oxidation was dominant attack mode and no considerable sulfidation occurred at 750 °C. The SiO₂ oxide was not characterized in the passive region because the thickness of the passive film was extremely thin, but was detected as the primary oxide in the localized corrosion region, where the selective oxidation of Al was observed by further progress of the corrosion attack front into the inner layer of coating.     

Cerium chemical conversion coatings for corrosion protection of stainless steels in hot seawater environments

In order to replace the hazardous chromate‐based surface treatment, a new cerium chemical conversion coating was developed on 316L stainless steel through a mixed solution of hydrated cerium nitrate, citric acid, and hydrogen peroxide. The chemical composition was characterized by energy‐dispersive spectroscopy, X‐ray photoelectron spectroscopy and atomic force microscope. The dense conversion coating is composed of CeO₂ with a small amount of Ce₂O₃ and has small grain size lower than 50 nm. Its thickness is about 47.4 nm as determined by spectroscopic ellipsometry analysis. Potentiodynamic polarization was used to study the corrosion behavior of the coatings in the concentrated artificial seawater at 72 °C. In comparison with the conventional nitric acid‐chromate passivated specimens, the cerium conversion coatings show much higher pitting potentials. It is suggested that the cerium conversion treatment is more effective than the nitric acid‐chromate passivation to improve the pitting resistance of 316L stainless steel used in the hot seawater environments.     

Characterization and corrosion behavior of ceramic coating on magnesium by micro-arc oxidation

In this study, the commercial pure magnesium was coated in different aqueous solutions of Na₂SiO₃ and Na₃PO₄ by the micro-arc oxidation method (MAO). Coating thickness, phase composition, surface and cross sectional morphology and corrosion resistance of coatings were analyzed by eddy current method, X-ray diffraction (XRD), scanning electron microscope (SEM) and tafel extrapolation method, respectively. The average thickness of the coatings ranged from 52 to 74 μm for sodium silicate solution and from 64 to 88 μm for sodium phosphate solution. The dominant phases on the coatings were detected as spinal Mg₂SiO₄ (Forsterite) and MgO (Periclase) for sodium silicate solution and Mg₃(PO₄)₂ (Farringtonite) and MgO (Periclase) for sodium phosphate solution. SEM images reveal that the coating is composed of two layers as of a porous outer layer and a dense inner layer. The corrosion results show the coating consisting Mg₂SiO₄ is more resistant to corrosion than that containing Mg₃(PO₄)₂.     

电解液组分对镁合金微弧氧化成膜及膜层耐蚀性的影响

基于单纯形重心设计改变Na₂SiO₃、NaOH、KF和NaAlO₂ 4种组分的搭配,在AZ91D镁合金上进行微弧氧化处理,研究了电解液配方对膜层成膜及耐蚀性能的影响。结果表明,所得到的回归方程非常显著,预测精度高。帕累托分析显示,4种电解质均对膜层耐蚀性影响显著。通过响应面分析可知,增大主盐Na₂SiO₃或者NaAlO₂的浓度可以显著提高膜层的耐蚀性。但二者复合却不利于耐蚀性的提高。主盐对于提高膜层成膜性及耐蚀性至关重要。当电解液中无主盐时,膜层的成膜性及耐蚀性都很差。当电解液中含有主盐时,适当增加NaOH与KF的浓度,膜层耐蚀性提高。通过Pearson相关分析可知,膜层耐蚀性主要受致密度及孔隙率的影响,同时也受膜厚、物相等其他特征参量的影响。而电解液各组分通过影响上述微观结构特征参量从而影响膜层性能。     

Influence of curing temperature, silica nanoparticles- and cerium on surface morphology and corrosion behaviour of hybrid silane coatings on mild steel

This work is aimed at developing and investigating silane based organic-inorganic hybrid coatings possessing unique properties, which can be used to improve the performance of steel structures subjected to marine corrosion. These silane based sol-gel coatings were prepared by dip coating planar samples of mild steel in solution of an organically modified silica sol made from hydrolysis and polycondensation of tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES) in acid catalysis condition. Crack-free coatings were obtained on curing at 200 °C. On increasing the curing temperature to 400 °C, however, cracks developed in the plain organic-inorganic hybrid coatings. This observation was consistent with the visual observations where appearance of the coated specimen changed from colourless metallic to brownish grey on curing from 200 °C to 400 °C temperature. The coatings were further modified using SiO₂ nanoparticles and cerium. The effect of change in the - temperature as well as - composition on the microstructural properties of the coatings was determined using optical microscopy, scanning electron microscopy and atom force microscopy. Additionally, Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR/FTIR) was carried out to show the formation of the Si-O-Si structural backbone of the hybrid material with the organic CH₃ group incorporated into the silica network. The corrosion protection performance of these coatings was examined using potentiodynamic polarisation technique and electrochemical impedance spectroscopy in aerated 3.5 wt.% NaCl solution. The polarization curves and corrosion resistance as measured by the bode plots suggested that the plain hybrid coatings offer good protection against corrosion. However, the SiO₂ and cerium modified nano hybrid coatings exhibited superior performance to that displayed by plain hybrid coatings.     

Study of the structure and corrosion behavior of PEO coatings on AM50 magnesium alloy by electrochemical impedance spectroscopy

In this work coatings were developed on the surface of AM50 magnesium alloy using four different electrolytes containing 10 wt.% each of K₃PO₄ and Na₃PO₄ in combination with either potassium or sodium hydroxides. Electrolyte conductivity and breakdown voltage were measured in order to correlate the property of the coating to the nature of electrolyte. Further, the coatings were examined using scanning electron microscopy for surface morphology and cross sectional investigation, X-ray diffraction for phase determination, and electrochemical impedance spectroscopy for corrosion resistance evaluation. The effect of employing different ions in the electrolytes results in different surface morphologies, chemical phases and, consequently, the corrosion resistance of the coatings. The EIS results indicate the presence of porous and compact layers in the structure of the PEO coatings, whilst the overall coating resistance mainly results from the compact layer, the role of the porous layer as a barrier against corrosion is negligible. Finally, a correlation between the passive current density of the bare alloy and the corrosion resistance of the PEO coating is proposed.