Effects of thermal and mechanical treatments on a titanium-based conversion coating for aluminium alloys

The influence of mechanical deformation and heating on the protective performance of a chromium-free conversion treatment for aluminium alloys has been assessed by polarisation and AC impedance measurements. Protection is unlikely to be seriously compromised by typical production operations.     

Ni对Zr-Cu-Al系非晶合金在NaCl溶液中腐蚀性能的影响

利用动电位极化和电化学阻抗谱研究了Ni元素对Zr-Cu-Al系非晶合金在3.5wt.%NaCl中性溶液中的电化学腐蚀行为的影响规律。结果表明：含Ni元素的Zr₅₅Cu₃₀Ni₅Al₁₀比Zr₅₅Cu₃₅Al₁₀非晶合金在NaCl溶液中具有更优异的耐腐蚀性能。Zr-Cu-Al系非晶合金在NaCl溶液中发生点腐蚀,圆形腐蚀坑内布满泡沫状孔洞。通过腐蚀前后的元素分布对比,发现Zr-Cu-Al非晶合金在Cl^_-作用下合金元素选择性溶解。含Ni元素的非晶合金形成致密的钝化膜,抑制了金属元素的选择性溶解,从而提高了耐腐蚀性能。研究结果可为耐Cl^_-环境腐蚀非晶合金成分设计及其应用提供参考。     

Improving the corrosion protection of aluminium alloys using reactive magnetron sputtering

Most high strength aluminium alloys used in the aircraft industries are susceptible to corrosion. Up to now hexavalent chromium is the conventional corrosion inhibitor. Because chromium in hexavalent state is carcinogenic, it is necessary to develop effective alternative inhibitor systems. We investigated magnetron sputtered substoichiometric and stoichiometric aluminium nitride (AlN_x with x ? 1) coatings for corrosion protection of aluminium alloys 2024-T3, 6061-T4 and 7075-T6. The corrosion behaviour of the treated surfaces was tested by anodic polarization scanning and salt spray testing.From the polarization curves it can be concluded that magnetron sputter coating with AlN_x leads to a higher pitting potential of the three aluminium alloys investigated. The salt spray tested samples also confirm the protective effect of the coatings. In addition we found that AlN_x layers with high nitrogen content lead to a stronger shifting in pitting potential than those with low nitrogen content. Anyway, the results of the salt spray testing show that particularly nitrogen-rich AlN_x layers are less stable towards NaCl electrolyte.     

Influence of alloying elements on electrochemical behaviour of ternary Al-Zn-Ga alloys for sacrificial anodes

Abstract

This work underlines the influence of alloying elements zinc and gallium on the electrochemical behaviour of aluminium alloys used as sacrificial anodes. Both the single and joint effects of these two elements on the free corrosion potential, the corrosion current density, and the development of the passive region were studied. Coupled potential and efficiency measurements were also carried out. It has been shown that the influence of gallium on the extent of the negative shift in corrosion potential of aluminium is greater than that of zinc. As regards the joint influence of the two elements, zinc was found to reduce the extent of the gallium induced negative shift in potential. Finally, for any composition the efficiencies were low, possibly because of partial segregation in these alloys.     

Investigation of the corrosion behaviour of steel coated with amorphous silicon carbon alloys

Thin amorphous silicon (a-Si:H) and carbonated silicon (a-Si_1 − xC_x:H) layers were deposited on stainless steel substrates using plasma-enhanced chemical vapour deposition (PECVD) in a “low-power” regime. The carbon content of the carbonated silicon (a-Si_1 − xC_x:H) alloys was varied between 0.1 and 0.37 at.%. The performance of these interfaces as effective corrosion barriers in 3% sodium chloride aqueous solutions was evaluated. Potentiodynamic polarisation curves and electrochemical impedance spectroscopy (EIS) were used next to X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) to investigate the protection efficiency of the different barriers. The a-Si:H coated showed better corrosion resistance as compared to the carbonated silicon alloys. No degradation was observed after 14 days immersion of the steel substrate coated with a-Si:H in 3% sodium chloride aqueous solution, making this coating an attractive candidate as corrosion barrier.     

Effect of common water contaminants on the corrosion of aluminium alloys in ethylene glycol-water solution

The effects of common water contaminants of chloride (Cl⁻), cupric (Cu²⁺) and ferric (Fe³⁺) ions, in four different mixture combination of Fe³⁺ + Cu²⁺, Cl⁻ + Fe³⁺, Cl⁻ + Cu²⁺ and Cl⁻ + Fe³⁺ + Cu²⁺, were examined on the corrosion behaviour of aluminium alloys in ethylene glycol-water solution, using mass loss technique. The highest material losses were recorded for the two alloys in ethylene glycol solution containing the combination of the chloride and the two heavy metal ions. The corrosivity of the solution in the presence of the combination of ions was in the order of Cl⁻ + Fe³⁺ + Cu²⁺ > Cl⁻ + Cu²⁺ > Cl⁻ + Fe³⁺ > Fe³⁺ + Cu²⁺. The results gave first-order kinetics with respect to aluminium in ethylene glycol solution-ion systems. Alloy 3SR exhibits maximum corrosion in all the solutions. It is concluded that the two commercial alloys in the solution polluted with all the three ions would not be able to survive for reasonable period of time without corrosion inhibitor.     

Deposition of HVAF-sprayed Ni-based amorphous metallic coatings

Ni₅₃Nb₂₀Ti₁₀Zr₈Co₆Cu₃ (at.%) amorphous alloy with high glass forming ability (GFA), capable of forming a wholly amorphous rod of 3 mm diameter by casting, was adopted to deposit amorphous metallic coatings by high velocity air fuel (HVAF) thermal spraying. The effects of powder feed rate and spraying distance on amorphous phase content and porosity of the coatings were investigated. It was indicated that an appropriate powder feed rate was desirable to produce a coating with high amorphous fraction, whereas a larger spraying distance led to a more dense coating. The corrosion resistance of the sprayed coatings was also examined in 1 M HCl aqueous solution.     

Application of niobium enriched ormosils as thermally stable coatings for aerospace aluminium alloys

The aim of this experimental research is to study the ability of niobium rich sol-gel coatings to withstand thermal stress, while remaining impermeable to corrosive agents for the protection of aluminium aerospace alloys. The coating material is developed via polymeric sol-gel synthesis employing 3-(trimethoxysilyl)propylmethacrylate (MAPTMS) and niobium ethoxide precursors as silicon and niobium sources, respectively. The beneficial effect of niobium inclusion within the coating was characterised spectroscopically, calorimetrically and electrochemically. The thermal cycling effects of the coating were studied using microscopic and accelerated test methods. Electrochemical tests showed that corrosion current of the niobium enriched material was 2 orders lower in magnitude than the equivalent MAPTMS coating. The neutral salt spray test results of the thermally stressed samples prove that inclusion of niobium nanoparticles within the silane matrix considerably improves the corrosion resistance performance.     

Influence of magnesium nitrate on the corrosion performance of sol-gel coated AA2024-T3 aluminium alloy

Traditional anticorrosion technology has relied heavily on using reducible metal species, predominantly hexavalent chromium (Cr(VI)), for protecting reactive metal alloys such as aluminium which is extensively used in the aerospace sector. However, the impending changes in the use of Cr(VI) in Europe and the United States have forced aerospace manufacturers to examine alternative materials for protecting aluminium. One of the most promising alternatives being investigated are organosilane based sol-gels containing anticorrosion additives. In this work the anticorrosion properties of magnesium (II) nitrate (Mg(NO₃)₂) as an inhibitor were investigated at different concentrations (0.1%-1.0 wt.%) in a methyltrimethoxysilane (MTEOS) sol-gel on the aluminium alloy AA 2024-T3 and compared to Alodine^TM 1200 (the established Cr(VI) pre-treatment). Electrochemical evaluation of the coating system by electrochemical impedance spectroscopy (EIS) and potentiodynamic scanning (PDS) measurements correlated strongly with results obtained from Neutral Salt Spray (NSS) exposure data. The surface morphology of the coating was studied using atomic force microscopy (AFM) and scanning electron microscopy (SEM) and Energy Dispersive X-ray Spectrometry (EDS). The results indicated that the optimum performance was achieved with a Mg (NO₃)₂ level of 0.7% w/w. It is proposed that the superior anticorrosion properties of the Mg²⁺ rich sol-gel are due to the pore blocking mechanism of insoluble magnesium precipitates formed during the hydrolysis process.     

Electrochemical response of AlNiLa amorphous and devitrified alloys

The electrochemical response of Al_94−xNi₆La_x alloys (x = 4, 5, 6, 7) after different stages of devitrification was studied in 0.05 M Na₂SO₄ as well as in different concentrations [0.001 M, 0.01 M and 0.1 M] NaCl solutions. Complementary crystallization studies were carried out to elucidate the composition dependent phase evolution in these alloys. It was observed that the primary crystallization did not cause any deterioration in the corrosion resistance of the alloys as compared to the amorphous alloys. In the case of Al₈₇Ni₆La₇, there was actually an improvement in the passivating ability in benign media. The various primary crystalline phases in the different alloys investigated did not cause different electrochemical responses. However, the onset of secondary crystallization caused a reduction in the corrosion resistance in the NaCl media through a loss in passivating ability of all the alloys. This is due to increased galvanic activity as well as the loss of the amorphous phase.     

Improving the corrosion performance of Cr-C amorphous coatings on steel substrate by modifying the steel surface preparation

Cr-C coating was electrodeposited on copper and steel substrates, using a trivalent chromium bath containing formic acid. Coatings produced had an amorphous cracked structure with a homogeneous granular morphology. The coated copper specimen showed passivation behaviour, but, the coated steel specimens revealed an active anodic behaviour. Evaluation of coatings produced on the steel substrate subjected to various surface preparations including mechanically polished, electropolished and anodically etched, showed a crack-free coating on the preanodically etched surface. Also, this coating had the lowest porosity, which provided the best protection and thus led to the lowest dissolution of the steel substrate.     

AlNx and a-SiOx coatings with corrosion resistance properties for dental implants

Aluminium nitride thin films were deposited on titanium fixtures, while silicon oxide thin films were deposited on titanium fixtures and chromium-cobalt substrates, using the RF magnetron sputtering technique. Each coating showed different corrosion behaviours when electrochemical characterisations were made in a simulated biological environment, i.e. Hank's solution. Although aluminium nitride was more effective in reducing the localised corrosion on titanium implants, silicon oxide showed the best behaviour against general corrosion and results were consistent for the two kinds of substrates. Moreover the application of a SiO₂/AlN bilayer onto the Ti fixtures improved the performances of each separate coating. When the coated surfaces were compared to uncoated substrates, there was no statistically significant difference in cell viability in the response of two different human osteoblastic cell lines — Saos-2 and MG-63. Field emission scanning electron microscopy assessed the surface morphology of coated and uncoated samples, whilst Fourier transform infrared spectroscopy was applied to investigate the bonding structure of barrier layers on silicon samples. On the basis of the data obtained, we are of the opinion that the tested materials show some promising characteristics for the fabrication of novel dental implants with reduced ion release properties.     

Influence of surface pre-treatments on disturbed rolled-in subsurface layers of aluminium alloys

Rolling is known to alter the surface properties of aluminium alloys and to introduce disturbed subsurface layers. These layers are characterised by a refined grain structure, rolled-in oxide particles, a fine distribution of intermetallic particles, various voids and cracks.In this study, the effects of some surface pre-treatments, i.e., alkaline etching at various temperatures and chemical cleaning with Nabuclean and CrO₃/H₃PO₄, on these rolled-in layers are investigated by means of surface analytical techniques. The changes in composition and morphology of the (sub)surface are studied with scanning electron microscopy/energy dispersive X-ray analysis and backscattered electron imaging (SEM/EDX + BEI). The presence of incorporated oxide particles is evaluated by measuring the total reflectance. The (re-)distribution of alloying, impurity and trace elements upon these surface treatments is investigated with radiofrequency glow discharge optical emission spectrometry (rf-GDOES).     

Corrosion resistance of cerium‐based chemical conversion coatings on AA5083 aluminium alloy

In this paper the effect of several parameters, such as temperature, time of immersion, cerium ions and hydrogen peroxide concentration, pH of the conversion solution, on the composition and morphology of the conversion layer are investigated as well as on its corrosion resistance in chloride environments. The cerium‐based chemical conversion coatings ennobles the corrosion potential and inhibits both the cathodic and anodic reactions rate. Using a cerium (III) chloride solution a not homogeneous coating is obtained and agglomerates with a “dry‐mud” morphology of mixed cerium‐aluminium oxide are deposited above the cathodic intermetallic particles, while using a cerium (III) nitrate solution the coating is more uniform but thinner than that obtained with cerium (III) chloride. Solution temperature below 50°C and time of immersion of 10 minutes produces a coating with better corrosion resistance.     

Determination of the protective properties of electrodeposited organic epoxy coatings on aluminium and modified aluminium surfaces

The electrochemical and transport properties and thermal stability of epoxy coatings electrodeposited on aluminium and modified aluminium surfaces (anodized, phosphatized and chromatized-phosphatized aluminium) have been investigated during exposure to 3% NaCl solution. From the results obtained from electrochemical impedance spectroscopy (EIS), gravimetric liquid sorption experiment and thermogravimetric analysis (TGA) it can be concluded that electrochemical and transport properties of epoxy coatings on anodized and chromatized-phosphatized aluminium are significantly improved with respect to the same epoxy coatings on aluminium and phosphatized aluminium: higher values of pore resistance and charge-transfer resistance and lower values of coating capacitance and double-layer capacitance, from EIS; smaller values of diffusion coefficient of water through epoxy coating, from sorption measurements and smaller amount of absorbed water inside the coating, from TGA. On the other hand, the somewhat lower thermal stability of these coatings was obtained.     

Corrosion inhibition of 7000 series aluminium alloys with cerium diphenyl phosphate

Cerium diphenyl phosphate (Ce(dpp)₃) has previously been shown to be a strong corrosion inhibitor for aluminium-copper magnesium alloy AA2024-T3 and AA7075 in chloride solutions. Surface characterisation including SEM and ToF-SIMS coupled with electrochemical impedance spectroscopy (EIS) measurements are used to propose a mechanism of corrosion inhibition which appears to involve the formation of a complex oxide film of aluminium and cerium also incorporating the organophosphate component. The formation of a thin complex film consisting of hydrolysis products of the Ce(dpp)₃ compound and aluminium oxide is proposed to lead to the observed inhibition. SEM analysis shows that some intermetallics favour the creation of thicker deposits predominantly containing cerium oxide compounds.     

The effects of nano-SiO2 additive on the zinc phosphating of carbon steel

In this paper, nano-SiO₂ was used as an accelerator for improving the microstructure and the corrosion resistance of phosphate coating on carbon steel. The chemical composition and microstructure of the coatings were analyzed by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). The effects of nano-SiO₂ on weight, roughness and corrosion resistance of the phosphate coatings were also investigated. Results show that the compositions of phosphate coating were Zn₃(PO₄)₂·4H₂O (hopeite), and Zn₂Fe(PO₄)₂·4H₂O (phosphophylite). The phosphate coatings became denser due to the addition of nano-SiO₂ which reduced the size of the crystal clusters. The average weight of phosphate coatings approximately linearly increased with the nano-SiO₂ content in the bath from 0 to 4 g/L, and the phosphate coatings formed in bath containing 2 g/L nano-SiO₂ showed the highest corrosion resistance in 5 wt.% sodium chloride solution at ambient temperature. Nano-SiO₂ would be widely utilized as a phosphating additive to replace the traditional nitrite, due to its less pollutant and its better quality of the coating.     

The synergistic inhibitive effect and some quantum chemical parameters of 2,3-diaminonaphthalene and iodide ions on the hydrochloric acid corrosion of aluminium

The effect of iodide ions on the inhibitive performance of 2,3-diaminonaphthalene (2,3-DAN) in 1 M HCl for aluminium corrosion has been studied using hydrogen evolution (gasometry) measurements at 30 and 40 °C. Results obtained showed that the presence of 2,3-DAN molecules in the corrosive medium (1 M HCl solution) inhibits the corrosion process of aluminium and as the concentration of 2,3-DAN increases the inhibition efficiency also increased at the studied temperatures. A synergistic effect was observed between KI and 2,3-DAN. The experimental results suggest that the presence of iodide ions in the solutions stabilized the adsorption of 2,3-DAN molecules on the metal surfaces and, therefore improve the inhibition efficiency of 2,3-DAN. Phenomenon of physical adsorption is proposed for the inhibition and the process followed the Freundlich adsorption isotherm. The activation energy (E_a), heat of adsorption (Q_ads) and free energy of adsorption for the corrosion process (ΔG_ads) have been evaluated at the different temperatures and the values support the results obtained. Some quantum chemical parameters and the Mulliken charge densities for 2,3-diaminonaphthalene were calculated by the AM1 Semi-empirical method to provide further insight into the mechanism of inhibition of the corrosion process.     

Influence of aluminium content on the dynamic characterstics of mischmetal based hydrogen storage alloys

Mischmetal (Mm) nickel (Ni) alloys with different aluminium (Al) contents are tested for hydrogen storage characteristics under dynamic operating conditions. The compositions considered are MmNi₅, MmNi_4.7Al_0.3, MmNi_4.5Al_0.5, MmNi_4.2Al_0.8 and MmNi₄Al. Pressure concentration isotherms (PCI), plateau slopes and absorption rates are measured. Activation energies are calculated by fitting Arrhenius equation to the absorption data. As expected, the plateau pressure of MmNi₅ decreased with increase in Al content. Apparent reaction enthalpy values (as distinct from enthalpy of formation calculated from static measurements), plateau slope, and activation energies increased, and absorption rate decreased with increase in Al content. The study confirms MmNi_4.5Al_0.5 as a preferred candidate for reversible hydrogen storage at room temperature with nominal supply pressure and fast kinetics.     

Protective ability of cerium-containing conversion films on aluminium

The options for electroless deposition of conversion films of lanthanum group metal oxides, in particular cerium, as an alternative to chromate conversion films (containing Cr⁶⁺) have been studied on aluminium. The main task of the study was to establish the influence of copper ions as a component of electrolytes for conversion treatment on the processes of formation and on the corrosion protective ability of cerium oxide films.

It has been ascertained that the electrochemical activation of the aluminium surface in the presence of Cu²⁺ in the electrolyte, leads to formation of oxide layers richer in cerium and possessing a better protective ability.

The presence of active cathodic sections of electroless, contact-deposited Cu has been shown to promote the corrosion activity of the system, due to the possibility of the appearance of micro-galvanic couples Al/Cu. A model experiment has been carried out to establish the inclination of the system to pitting corrosion. It has been shown that at the studied concentration of Cu²⁺ in the electrolyte the character of the corrosion does not change observably but there is a catalysing effect of the copper ions in the working electrolyte. The copper islands on the Al surface also have a catalysing effect, which is dominating in the processes of cerium oxide film formation. The chemical state and the composition of the conversion films have been defined by XPS measurements.