Active corrosion protection of various aluminium alloys by lithium-leaching coatings

This study presents the active protective properties of lithium-leaching coatings for a range of aluminium alloys. Coatings with and without lithium carbonate as leachable inhibitor were applied on the aluminium alloys, artificially damaged and exposed to the neutral salt spray. A combined approach of scanning electron microscopy and electrochemical measurements revealed that the lithium carbonate leaching coating provided effective corrosion inhibition on AA2024, AA7075, AA5083, and AA6014 by the formation of a protective layer in the defect area and preventing local corrosion processes despite the different intrinsic electrochemical activity of the alloys.     

Investigation of filiform corrosion of coated aluminium

Filiform corrosion on different aluminium alloys, coated with a clear varnish has been studied. Image analysis and metallographies were used to characterize the corrosion. It has been shown, that filiform corrosion consists of a lateral propagation of filaments and an attack on the aluminium under the filaments. The extent of filiform corrosion is dependent on the sort of alloy and the pretreatment of metall surfaces.     

The effect of trace additions of copper and pretreatment conditions on the filiform corrosion of powder-coated aluminium alloy AA6060

This paper presents a short review of the literature data and the newest studies of filiform corrosion (FFC) testing of profiles extruded using a recycling-friendly AA 6xxx aluminium alloy, with Cu content up to 0.09 wt%. As the pretreatment plays a significant role in avoiding FFC on powder-coated aluminium profiles, the profiles were pretreated and coated at three different production sites. They have been tested at 40°C, 82% RH for 1000 hours (according to modified ISO 4623-2). It was observed that differences in FFC behaviour of the same type of profile coated at different plants were more significant than differences between samples with increasing Cu content. In order to understand the differences between profiles coated at different sites, GDOES analysis of samples was performed, specially focusing on surface enrichment of copper through the pretreatment.     

Experimental correlation between metallographic evaluation and electrochemical noise in intergranular corrosion tests of aluminium alloys

In the present work, the correlation between the metallographic evaluation and electrochemical noise (EN) in intergranular corrosion (IGC) tests of aluminium alloy 2024‐T3 has been analysed. For this purpose, the influence of temperature and hydrogen peroxide concentration on the IGC attack has been studied. Similar IGC was observed between 20 and 40 °C, showing a low dependence with temperature (at least in this range). Hydrogen peroxide was seen to have a strong effect, leading to IGC activation when raising its concentration. The results of the detailed metallographic evaluation of the samples after the tests were analysed together with the EN measured during the tests. The averaged noise resistance was inversely proportional to the depths of the attacks, whereas the average of the parameter so‐called ‘Statistical Noise Power’ was directly related to the IGC degree. The metallographic evaluation and the EN showed a reasonable experimental correlation. Copyright © 2012 John Wiley & Sons, Ltd.     

XPS study of the effect of aluminium on the atmospheric corrosion of the AZ31 magnesium alloy

The surface characteristics and corrosion behaviour of the AZ31 magnesium alloy exposed to a high relative humidity (RH) atmosphere were investigated. During the first 15 days of humidity test at 98% RH and 50 °C, a significant increase of magnesium carbonate and a decrease of magnesium oxide were detected on the surface film by XPS; after this stage, increased exposure times did not produce substantial changes on the relative amounts of these compounds. The surface film of commercially pure magnesium, also examined for comparison purposes, revealed more magnesium carbonate and less magnesium oxide compared with the AZ31 alloy. Unlike the AZ31 alloy, the surface of pure Mg disclosed almost complete substitution of MgO by magnesium carbonate after 30 days of exposure time. Mass gain values of tested specimens and scanning electron microscope characterisation of corroded surfaces indicated lower corrosion susceptibility of the AZ31 alloy compared with the commercially pure Mg, suggesting superior chemical stability of the oxide/hydroxide film formed over the magnesium–aluminium alloy surface. XPS and energy dispersive X‐ray (EDX) analyses did not revealed any substantial enrichment of aluminium in the corrosion products film on the AZ31 alloy after 30 days of testing. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface analysis and corrosion resistance of new nickel base thin film alloys

Electroless Zn–Ni–P thin films were deposited on low carbon steel from an alkaline non‐cyanide aqueous electrolyte. The newly developed ternary alloys structure and microstructure investigations were carried out via X‐ray diffraction and SEM. Chemical composition of the coatings was investigated via energy dispersive spectroscopy. Polarization tests were used to study the corrosion properties of the coatings in a 3.5 wt.% NaCl solution. The results confirmed the high corrosion resistance of Zn–Ni–P alloy plated steel sheet. The surface analysis of the thin film samples before and after corrosion was performed by XPS. The incorporation of Zn in Ni–P thin film is proven for all initial samples to be as a mixture of zinc and zinc oxide, while nickel exists in +2 and +3 oxidized states. A passive film of a mixture of oxide and hydroxide of zinc and nickel forms on the surface and prevents the Zn–Ni–P thin films from corrosion. Copyright © 2014 John Wiley & Sons, Ltd.     

Crack‐free sol‐gel coatings for protection of AA1050 aluminium alloy

Organically modified sol‐gel coatings have been investigated as potential replacements for chromate conversion treatments of an AA1050 aluminium alloy. The coatings were prepared by combination of a completely hydrolysable precursor of tetra‐n‐propoxyzirconium (TPOZ), with a partially hydrolysable precursor of glycidoxypropyltrimethoxysilane (GPTMS). GPTMS contains an organic functional group, which is retained in the sol‐gel coatings after the hydrolysis–condensation process. Different GPTMS/TPOZ ratios and withdrawal speeds were studied. Coatings produced using a low GPTMS/TPOZ ratio and a high withdrawal speed generated significant cracks due to the shrinkage of the coatings, with no corrosion protection of the alloy. It was found that increase of organic moieties reduced the shrinkage of the coatings and the tendency for crack formation. By control of process parameters and ratios of organic and inorganic moieties, crack‐free sol‐gel coatings above 1 µm thick, with improved corrosion protection, can be produced on the alloy surface. Copyright © 2010 John Wiley & Sons, Ltd.     

Determination of P/Al ratio in phosphorus-doped aluminium oxide thin films by XRF,RBS and FTIR

Phosphorus-doped aluminium oxide thin films were deposited in a flow-type ALE reactor from AlCl₃, H₂O and from either P₂O₅ or trimethyl-phosphate. Structural information of the films was obtained from Fourier transform infrared (FTIR) spectra. Rutherford backscattering spectroscopy (RBS) was used to quantitatively determine the composition of the films. The P/Al intensity ratios calculated from X-ray fluorescence (XRF) results were in a linear relation with the P/Al concentration ratios calculated from RBS results. For comparison, the intensity ratios of the phosphorus peak (P=O) at about 1250 cm^–1 and the aluminium peak (Al-O) at about 950 cm^–1 were determined from the IR absorption spectra. The calibration of FTIR peak intensities was done by plotting the intensity ratios of phosphorus and aluminium peaks against the P/Al concentration ratios measured by RBS. FTIR gave also a linear calibration curve with RBS but the method is less suitable for routine analysis of P/Al ratio than XRF.     

Correlation between hydroxyl fraction and O/Al atomic ratio as determined from XPS spectra of aluminium oxide layers

A set of five different aluminium oxide layers has been investigated using XPS. The oxide layers were made by oxidizing aluminium in a vacuum, with an alkaline and acidic pretreatment and in boiling water. Hydroxyl fractions of the aluminium oxide layers ranging from 0.0 to 0.5 were determined by constrained curve-fitting of the O 1s peak. The O/Al atomic ratios of the aluminium oxide layers, ranging from 1.5 to 2.0, were determined from the O 1s and Al 2p photoelectron intensities. A method is presented to account for the attenuation of the photoelectron intensities by the contamination overlayer. For the studied oxide layers, a linear relation is observed between the hydroxyl fraction and the O/Al atomic ratio of the aluminium oxide layers. It is concluded that the results obtained by the curve-fitting procedure are reliable. Furthermore, a linear relation is observed between the hydroxyl fraction and the O 1s peak width. The O 1s binding energies of the O²⁻ and OH⁻ components of the oxide layers correspond to 531.0 ± 0.1 eV and 532.4 ± 0.1 eV, respectively. Only pseudoboehmite showed 0.5 eV lower binding energies for these components. Angle-resolved XPS analysis showed that most of the studied oxides are enriched in hydroxyl groups at their outermost surface. Copyright © 2004 John Wiley & Sons, Ltd.     

Evolution of surface characteristics of two industrial 7xxx aluminium alloys exposed to humidity at moderate temperature

This study analyses the evolution of surface characteristics of two industrial high-strength 7xxx aluminium alloys with a focus on alloy composition and environmental parameters. Based on storage and transport conditions of as-machined products, the effect of humidity—as liquid and vapour phase—on the natural oxide layer has been studied. The evolution of the natural oxide layer has been analysed by scanning electron microscopy and X-ray photoelectron spectroscopy. The growth behaviour of the surface layer is dominated by environmental conditions, while microgalvanic activity depends mainly on the alloys' chemical composition and differs significantly for tested alloys. Scanning transmission electron microscopy images demonstrated that the long-term exposure at moderate temperatures affects the microstructure near the surface, which differs for the analysed alloy compositions. An anomalous precipitation of zinc-rich particles at the surface and along the precipitate-free zone is observed for the alloy with higher Zn/Mg ratio and lower Cu content.     

Surface properties of metal alloys used in aviation after plasma treatment

The metal alloys: aluminum AMS 4037, 4041, 4049, carbon steel AMS 5045, titanium alloy AMS 4911 and cadmium steel used in aviation were treated by air and argon plasmas. For their activation, low pressure plasma was used. Surface treatment caused a significant increase of wettability due to the increasing surface roughness and introduction of polar functional groups onto the surface. Changes of surface properties are reflected by the value of electron donor parameter of apparent surface energy. Copyright © 2017 John Wiley & Sons, Ltd.     

Monitoring corrosion and corrosion control of low alloy ASTM A213 grade T22 boiler steel in HCl solutions

Rates of corrosion of low alloy ASTM A213 grade T22 boiler steel were monitored in aerated stagnant 0.50 M HCl solutions at different temperatures (283–303 K) using Tafel extrapolation method and the non-destructive electrochemical frequency modulation (EFM) technique, complemented with XPS examinations. Serine (Ser) was introduced as a corrosion-safe inhibitor. Corrosion rates (in μm y^?1) obtained from these two methods was in good agreement. Tafel plots showed that Ser acted mainly as a cathodic-type inhibitor. The inhibition process was attributed to the formation of an adsorbed film on the metal surface that protects the metal against corrosive agents. XPS examinations of the electrode surface confirmed the existence of such adsorbed film. The inhibition efficiency increased with increase in Ser concentration, while it decreased with temperature, suggesting physical adsorption. Activation energies have been calculated in the absence and presence of various concentrations of Ser by measuring the temperature dependence of the corrosion rate obtained from the two methods employed. It was found that the activation energy in the presence of Ser is higher than that in bare HCl solution. The adsorptive behaviour of Ser followed Temkin-type isotherm. The standard free energy of adsorption was estimated to be ?25 kJ mol^?1 at 303 K. These results confirmed the occurrence of physical adsorption.     

Influence of alloying elements and etching treatment on the passivating films formed on aluminium alloys

This paper studies the characteristics of aluminium oxide layers present on the surface of commercial aluminium specimens after thermomechanical processing and after subsequent etching in an alkaline solution, highlighting the main differences observed. An attempt is made to establish possible relationships between alloying elements and the characteristics of these layers. Copyright © 2006 John Wiley & Sons, Ltd.     

Deposition of polysiloxane‐like nanofilms onto an aluminium alloy by plasma polymerized hexamethyldisiloxane: characterization by XPS and contact angle measurements

In this work, aluminium (Alclad 2024‐T3) substrates were cleaned by an r.f. (13.56 MHz) plasma, using argon (Ar), oxygen (O₂) and a mixture of O₂/Ar (50:50) gases. The effectiveness of plasma cleaning was checked in situ using X‐ray photoelectron spectroscopy (XPS) and ex situ using water contact angle measurements. XPS O/Al surface atomic ratios are in excellent agreement with those of the crystalline boehmite and the pseudoboehmite. Oxygen O 1s peak‐fitting was used to quantify the proportion of hydroxyl ions and the functional composition on the aluminium surface: the surface cleaned with O₂ plasma contains 50% of aluminium hydroxides, the ones cleaned with Ar plasma and with Ar/O₂ plasma contain, respectively, 25 and 37% hydroxyl ions. The binding energy separation between Al 2p and O 1s is characteristic of AlO(OH). Thin SiO_x films were subsequently deposited from a mixture of hexamethyldisiloxane (HMDSO) and oxygen. In the absence of oxygen, a hydrophobic (Θ≥ 100° ) film characteristic of polydimethylsiloxane (PDMS) is formed: polysiloxane‐like thinner films (SiO_x) are obtained with the introduction of oxygen. XPS and contact angle measurements confirmed both the composition and the structure of these films. More importantly, contact angle measurements using different liquids and interpreted with the van Oss‐Good‐Chaudhury theory allowed determination of the surface free energy of the deposited films: the calculated values of surface tension of the film formed from HMDSO/O₂: (50/50) are in excellent agreement with those of reference silica‐based materials such as a silicon wafer and cleaned glass. Copyright © 2007 John Wiley & Sons, Ltd.     

Corrosion behaviour of mechanically polished AA7075‐T6 aluminium alloy

In the present study, the effects of mechanical polishing on the microstructure and corrosion behaviour of AA7075 aluminium alloy are investigated. It was found that a nano‐grained, near‐surface deformed layer, up to 400 nm thickness, is developed due to significant surface shear stress during mechanically polishing. Within the near‐surface deformed layer, the alloying elements have been redistributed and the microstructure of the alloy is modified; in particular, the normal MgZn₂ particles for T6 are absent. However, segregation bands, approximately 10‐nm thick, containing mainly zinc, are found at the grain boundaries within the near‐surface deformed layer. The presence of such segregation bands promoted localised corrosion along the grain boundaries within the near‐surface deformed layer due to microgalvanic action. During anodic polarisation of mechanically polished alloy in sodium chloride solution, two breakdown potentials were observed at ?750 mV and ?700 mV, respectively. The first breakdown potential is associated with an increased electrochemical activity of the near‐surface deformed layer, and the second breakdown potential is associated with typical pitting of the bulk alloy. Copyright © 2009 John Wiley & Sons, Ltd.     

SEM and RBS characterization of a cobalt‐based conversion coating process on AA2024‐T3 and AA7075‐T6

Samples of aluminium alloys AA2024‐T3 and AA7075‐T6 were treated with a chromate‐based deoxidizer, then conversion coated with a commercial cobalt‐based solution and finally sealed with a commercial vanadate‐based product. The alloy specimens were examined using scanning electron microscopy, transmission electron microscopy and Rutherford backscattering spectroscopy. The thickness of the cobalt‐based conversion coating increased rapidly up to 5 min of immersion but more slowly for longer times. Sealing resulted in penetration of vanadium through the oxide and a small increase in thickness due to the deposition of a thin sealing coating within the pores and on the external surface of the cobalt‐containing coating. Copyright © 2004 John Wiley & Sons, Ltd.     

XPS imaging investigations of pitting corrosion mechanisms in Inconel 600

The surface chemistry associated with pitting corrosion on a nickel‐based alloy, Inconel 600, has been studied using imaging x‐ray photoelectron spectroscopy. The irregularity of the sample surfaces necessitated a more elaborate background correction than is usually applied in such imaging. Areas of active pitting were found to contain corrosion products that are high in chromium oxide and depleted in nickel and iron. Sites of anodic activity on the surface were able to be defined more clearly using principal component analysis. Elements that are dissolved preferentially are deposited cathodically within well‐defined regions whose distance from the anodic pit appears related to the open‐circuit potential. Copyright © 2005 John Wiley & Sons, Ltd.     

Effects of thermal treatment on hydrophilicity and corrosion resistance of Ti surface

Surface treatment of titanium (Ti) surface has been extensively studied to improve its properties for biomedical applications, including hydrophilicity, corrosion resistance, and tissue integration. In this present work, we present the effects of thermal oxidation as surface modification method on metallic titanium (Ti). The Ti foils were oxidized at 300°C, 400°C, 500°C, and 600°C under air atmosphere for 3 hours, which formed oxide layer on Ti surface. The physicochemical properties including surface chemistry, roughness, and thickness of the oxide layer were evaluated in order to investigate how these factors affected surface hydrophilicity, microhardness, and corrosion resistance properties of the Ti surface. The results revealed that surfaces of all oxidized samples were modified by formation of titanium dioxide layer, of which morphology, phase, and thickness were changed according to the oxidized temperatures. Increasing oxidation temperature led to the formation of thicker oxide layer and phase transformation of anatase to rutile. The presence of the oxide layer helped the improvement of corrosion resistance and microhardness. The most improvement in surface roughness was found in the specimens treated at 400°C, which significantly improved surface hydrophilicity. But both surface roughness and hydrophilicity reduced when oxidized at 500°C and 600°C, suggesting that hydrophilicity was dominated by the surface roughness. In addition, this surface treatment did not reduce the biocompatibility of the metallic Ti substrates against murine osteoblasts (MC3T3).     

Adsorption of phenyl phosphate on Ni-Cr alloy surface: Experimental and theoretical investigations

The adsorption behaviour of phenyl phosphate, which is an available biomolecule, on NiCr alloys was investigated. Atomic flame spectroscopy was used to characterize the elemental dissolution during immersion in neutral aqueous solution of 0.09 w% sodium chloride, 37°C. Phenyl phosphate is shown to reduce the release of both Ni²⁺ and Cr³⁺ ions. XPS analyses evidence the formation of a passive film which is mainly consisted in dichromium trioxide and an ultrafilm layer of phenyl phosphate is adsorbed at the passive film surface. DFT+U calculations show that the phenyl phosphate self-assembling at a Cr₂O₃ surface is thermodynamically favoured, with calculated adsorption energy of 2.9 eV. The first half of this value is due to the interaction with the surface, and the second one is due to self-assembling. This study suggests that phenyl phosphate has an important capacity to prevent, in neutral liquid environment, the release of Cr-Ni surface ions thanks to self-assembling in an inner sphere adsorption on the passive film surface. The phosphate group is covalently anchored to the surface. However, the phenyl ring has two roles: (i) it strongly contributes to the self-assembling and (ii) it acts as a hydrophobic function.     

Comparative study of self‐assembly of a range of monofunctional aliphatic molecules on magnetron‐sputtered aluminium

The adsorption of a range of organic molecules from toluene onto the oxidized surface of magnetron‐sputtered aluminium metal is studied using sessile drop water contact angle measurements. Molecules with different head group functionalities and various chain lengths are considered, including alkyl carboxylic acids, alkyl phosphonic acids, alkyl amines, alkyl trimethoxysilanes, alkyl trichlorosilanes and epoxy alkanes. Alkyl phosphonic and carboxylic acids are identified as readily forming the most well‐packed monolayers on the aluminium surface, whereas the others adsorb less well and the chlorosilanes polymerize as a result of combination with moisture to form a thick deposit. The high‐adsorption‐density monolayers of alkyl phosphonic and carboxylic acids were studied using polarization modulation infrared reflection–absorption spectroscopy (PM‐IRRAS) and x‐ray photoelectron spectroscopy (XPS): PM‐IRRAS reveals relatively poorer ordering of the C₁₀ alkyl carboxylic acid monolayer compared with that formed from the phosphonic acid, and XPS data suggest that this is likely to relate to a lower ability to displace preadsorbed volatile organic compounds. Copyright © 2004 John Wiley & Sons, Ltd.