Growth and real time corrosion resistance monitoring of lead decanoate coatings

Lead is very susceptible to corrosion in the presence of organic acids and humidity. A potential countermeasure is to apply a lead carboxylate coating by immersing the metal in a sodium carboxylate solution/suspension. In this work we report on the degree of surface coverage and the corrosion resistance of a lead decanoate Pb(C₁₀)₂ coating as a function of treatment time. Results show that the surface coverage reaches 91% after 15 min and about 100% after 1 h in a 0.05 M sodium decanoate solution. The corrosion resistance, as indicated by electrochemical impedance spectroscopy, continues to increase even after 6 h of immersion. In addition, we show that in the case of planar transport, a diffusion layer of 17 mm thickness exists, wherein the sodium decanoate concentration drops linearly from its bulk value to almost zero at the solid/surface interface.     

The effect of some triazole derivatives as inhibitors for the corrosion of mild steel in 1 M hydrochloric acid

Corrosion inhibition by some new triazole derivatives on mild steel in 1 M hydrochloric acid solutions has been investigated by weight loss test, electrochemical measurement, scanning electronic microscope analysis and quantum chemical calculations. The results indicate that these compounds act as mixed-type inhibitors retarding the anodic and cathodic corrosion reactions and do not change the mechanism of either hydrogen evolution reaction or mild steel dissolution. The studied compounds following the Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The effect of molecular structure on the inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were calculated.     

Effect of La surface treatments on corrosion resistance of A3xx.x/SiCp composites in salt fog

The influence of the SiC_p proportion and the matrix concentration of four aluminium metal matrix composites (A360/SiC/10p, A360/SiC/20p, A380/SiC/10p, A380/SiC/20p) modified by lanthanum-based conversion or electrolysis coating was evaluated in neutral salt fog according to ASTM B 117. Lanthanum-based conversion coatings were obtained by immersion in 50 °C solution of La(III) salt and lanthanum electrolysis treatments were performed in ethylene glycol mono-butyl ether solution. These treatments preferentially covered cathodic areas such as intermetallic compounds, Si eutectic and SiC_p. The kinetic of the corrosion process was studied on the basis of gravimetric tests. Both coating microstructure and nature of corrosion products were analyzed by scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray analysis (EDS) and low angle X-ray diffraction (XRD) before and after accelerated testing to determine the influence of microstructural changes on corrosion behaviour during exposure to the corrosive environment. The corrosion process was more influenced by the concentration of alloy elements in the matrix than by the proportion of SiC_p reinforcement. Both conversion and electrolysis surface treatments improved the behaviour to salt fog corrosion in comparison with original composites without treatment. Additionally, electrolysis provided a higher degree of protection than the conversion treatment because the coating was more extensive.     

Electrochemical and quantum chemical studies of some Schiff bases on the corrosion of steel in H2SO4 solution

The efficiency, as steel-corrosion inhibitors in 0.1 M and 1 M H₂SO₄, of two Schiff bases, 2-{[(4-methoxyphenyl)imino]methyl}phenol and 1-{[(4-methoxyphenyl)imino]methyl}-2-naphthol, (abbreviated SB-1 and SB-2, respectively) was investigated by Tafel extrapolation and linear polarization methods. Corrosion parameters and adsorption isotherms were determined from current-potential curves. It was found that the percent inhibition efficiencies (η%) and surface coverage (θ) increase with an increases in the concentrations of inhibitors. The results showed that these compounds act as good corrosion inhibitors especially at high concentrations. The adsorption of used compounds on the steel surface obeys Langmuir's isotherm. Obvious correlation was found between corrosion inhibition efficiency and quantum chemical parameters obtained by B3LYP/6-31g(d) method. The obtained theoretical results have been compared with the experimental findings.     

A combined study of the oxidation mechanism and resistance of AISI D6 steel exposed at high temperature environments

In this work it is thoroughly examined the oxidation performance of D6 tool steel under isochronal and isothermal oxidations. Isochronal oxidation tests, from ambient temperature to 1000 °C, revealed the oxidation rate of the coupons at different temperatures. Four different temperatures were selected for the isothermal oxidation test, which correspond to different oxidation rates. The oxidation and the examination of the samples were accomplished by thermogravimetric analysis (TG) in air with which the mass gain of the samples due to oxidation was simultaneously acquired. The samples were, also, examined by scanning electron microscopy (SEM), in order to observe their surface before and after the oxidation tests. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used for the accurate identification of the as formed oxides. The results revealed that in every case two distinct layers of oxides were formed while their composition was different, depending on the temperature of oxidation. Furthermore, the thickness of the as formed oxides is increased when the oxidation is performed at higher temperatures.     

Stress corrosion cracking behavior of Nd:YAG laser-treated aluminum alloy 7075

Nd-YAG laser surface treatment was conducted on 7075-T651 aluminum alloy with the aim of improving the stress corrosion cracking resistance of the alloy. Laser surface treatment was performed under two different gas environments, air and nitrogen. After the laser treatment, coarse constituent particles were removed and fine cellular/dendritic structures had formed. In addition, for the N₂-treated specimen, an AlN phase was detected. The results of the stress corrosion test showed that after 30 days of immersion, the untreated specimen had been severely attacked by corrosion, with intergranular cracks having formed along the planar grain boundaries of the specimen. For the air-treated specimen, some relatively long stress corrosion cracks and a small number of relatively large corrosion pits were found. The cracks mainly followed the interdendritic boundaries; the fusion boundary was found to be acting as an arrestor to corrosion attacks. In contrast, only few short stress corrosion cracks appeared in the N₂-treated specimen, indicating an improvement in corrosion initiation resistance. The superior corrosion resistance was attributed to the formation of the AlN phase in the surface of the laser-melted layer, which is an electrical insulator. The electrochemical impedance measurements taken during the stress corrosion test showed that the film resistance of the laser-treated specimens was always higher than that of the untreated specimen, with the N₂-treated specimen showing the highest resistance.     

Examination of the oxidation resistance of high-alloyed tool steels at elevated temperatures

In the present work the structure of two different tool steels is examined before and after oxidation up to 1000 °C in air. The materials under examination have different chromium contents. Also, the first contains vanadium (S1 tool steel) and the second tungsten (S2 tool steel) as alloying element, while the rest are common. The examination took place by thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy and X-ray diffraction. From this study it is deduced that the structure of the two steels, before oxidation, has several distinguishing differences mostly in the chromium distribution in the iron matrix. The oxidation tests revealed that S2 oxidizes at higher temperatures than S1, but finally, at 1000 °C, S2 tool steel has greater mass gain, because it oxidizes at a higher rate.     

Adsorption and film growth of N-methylamino substituted triazoles on copper surfaces in hydrocarbon media

The adsorption of benzotriazole (BTA), tolyltriazole (TTA) and two different N-methylaminosubstituted triazoles on copper surfaces in hydrocarbon media has been examined by in situ ellipsometry and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). All four triazoles were found to form films and from the ellipsometric study were the film thicknesses estimated to be in the range of 0.5-2 nm after 1000 min exposure time. The layers formed from BTA and TTA were thicker (up to 2 nm) than the layers from N-aminomethyl substituted triazoles (roughly 0.5 nm). Desorption was studied qualitatively and 20% or less of the adsorbed material were found to desorb. The ToF-SIMS study showed that while BTA and TTA adsorbed intact did the N-aminomethyl substituted triazoles appear to loose their aminomethyl tails on binding since only signals corresponding to triazole moieties of the compounds were detected.     

Assessing defect density and wear resistance of ultrathin diamond-like carbon films

Diamond-like carbon (DLC) films serve the dual purpose of protecting the magnetic underlayer from both slider contact and environmental corrosion in computer disk drives. Steadily increasing storage densities necessitate thinner and thinner protective films. Continuous, pinhole-free coverage of the magnetic medium is more difficult to achieve with thinner layers. Due to their sub-nanometer size, conventional techniques (SEM and AFM) are generally unable to detect pinholes. Therefore, we have utilized a novel pinhole-decoration technique (based on electrodeposition of Cu) to assess the coverage of very thin dual ion beam deposited nitrogen-doped DLC (N-DLC) films. The results of the decoration technique are compared with nanoscratch wear-resistance data. This combination of techniques demonstrates that, below 2 nm, the layer continuity and nanoscratch wear resistance of N-DLC films are severely compromised. Received: 5 September 2001 / Accepted: 11 December 2001 / Published online: 20 March 2002     

Microstructure and Corrosion Performance of Oxide Coatings on Aluminium by Plasma Electrolytic Oxidation in Silicate and Phosphate Electrolytes

Ceramic coatings are fabricated on pure aluminium by plasma electrolytic oxidation （PEO） in three kinds of electrolyte systems [E1： 0.05M NaOH＋0.033M Na2SiO3, E2： 0.025M NaOH＋0.008M （NAPO3）6 and E3： 0.025M NaOH＋0.066M Na2SiO3＋0.008M （NAPO3）6]. The voltage-time responses show that the PEO process of E2 has the highest discharging voltage, which results in the biggest pores and heaviest cracks on the surfaces. X-ray diffraction results show that coatings produced in E1 and E3 are mainly composed of γ-Al2O3 and mullite, while coatings produced in E2 are mainly composed of a-Al2O3. After PEO treatment the corrosion resistance of aluminium is improved significantly and the coatings produced in E3 perform the best corrosion resistance.     

Structural characterization and properties of lanthanum film as chromate replacement for tinplate

Sulfide-stain resistance of La-passivated, unpassivated and Cr-passivated tinplate was measured using a cysteine tarnish test. Corrosion behavior of these tinplates was investigated using electrochemical impedance spectroscopy (EIS) measurement. The morphology, composition and thickness of lanthanum film were studied by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray fluorescence spectrometry (XRF), respectively. La-passivation treatment remarkably enhances sulfide-stain resistance of tinplate, and sulfide-stain resistance of La-passivated tinplate is slightly higher than that of Cr-passivated tinplate. La-passivation treatment also significantly improves corrosion protection property of tinplate. In contact with 3.5% NaCl solution, corrosion resistance of La-passivated tinplate is close to that of Cr-passivated tinplate, and in contact with 0.1 M citric-citrate buffer solution, corrosion resistance of La-passivated tinplate is higher than that of Cr-passivated tinplate. Lanthanum film is composed of spherical particles about 50-1000 nm in diameter, while most part of tinplate's surface is covered with the small particles about 50-200 nm. The film mainly consists of lanthanum and oxygen, which mainly exist as La₂O₃ and its hydrates such as La(OH)₃ and LaOOH. The amount of lanthanum in the film is about 0.0409 g/m².     

A novel process of electroless Ni-P plating with plasma electrolytic oxidation pretreatment

A novel Ni based coating - plasma electrolytic oxidation (PEO) pre-treatment followed by electroless nickel (EN) plating - has been developed to produce pore free Ni coatings on AZ91 magnesium alloy. The application of the PEO film between the nickel coating and the substrate acts as an effective barrier and catalytic layer for the subsequent nickel plating. The potentiodynamic tests indicated that the corrosion current density of the PEO + EN plating on AZ91 decreased by almost two orders of magnitudes compared to the traditional EN coating. Salt fog spray testing further proved this improvement. More importantly, the new technique does not use Cr⁺⁶ and HF in its pretreatment, therefore is a much environmentally friendlier process.     

Ultra-Thin Silicon Carbon Nitride Film: a Promising Protective Coating for Read/Write Heads in Magnetic Storage Devices

Ultra-thin amorphous Si C-N films, down to 2nm, have been synthesized by MW-ECR plasma enhanced unbalanced magnetron sputtering. The friction coefficient of the film is only 0.11, determined in dry friction tests against the GCr15 ball at a load of 400mN for 20min. The films exhibit good protection against corrosion when they are immersed in a more severe corrosion environment of 0. 1 mol/L oxalic acid for 12 h compared to the usual conditions （0.05 mol/L, 4min） used in current computer industries. These good properties can be attributed to the smooth, dense and pore free structure of the film. These indicate that the Si-C-N film synthesized by the present technique may be a promising protective coating for read/write heads and other magnetic storage devices.     

Fundamental processes of aluminium corrosion studied under ultra high vacuum conditions

Surface sensitive electron spectroscopy was applied to study the fundamental processes of aluminium corrosion. We used metastable induced electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy (UPS) for the investigation of the densities of states of surface and bulk, respectively. Furthermore we applied X-ray photoelectron spectroscopy (XPS) to investigate the chemical composition of the top surface layers. All measurements were performed under ultra high vacuum conditions.Al films with thicknesses of 7 nm were investigated. Both the interaction of oxygen and water with these films leads to the formation of an aluminium-oxygen layer, which is partly composed of stoichiometric Al₂O₃. Weak heat treatment at 770 K transforms the surface layer into Al₂O₃ with a thickness of about 2 nm. Further gas offer does not lead to an increase of this thickness, neither for oxygen nor for water. Additional to the oxygen offer, water exposure leads to the formation of OH species in the top aluminium-oxygen layer to a small amount. Weak heat treatment to 770 K removes this species completely. Water exposure leads to a much faster oxide formation than oxygen exposure. We try to give a model for the fundamental corrosion processes on a molecular scale.     

The effect of pH and role of Ni in zinc phosphating of 2024-Al alloy: Part II: Microscopic studies with SEM and SAM

Coatings formed on 2024-T3 aluminum alloy were studied by scanning electron microscopy (SEM) and scanning Auger microscopy (SAM) after dipping in zinc phosphating (ZPO) baths at different acidities, with or without the Ni²⁺ additive. The objective was to learn more about the ZPO coating mechanism on the different microstructural regions of 2024-T3. When the initial coating solution pH is 4 (optimal acidity), a slower etching rate at the Al-Cu-Fe-Mn intermetallic particle causes significant precipitation of ZnO, which differs from the coating on other regions of the surface where phosphate predominates. The larger crystals (∼μm dimension) on the matrix and the Al-Cu-Mg particle contain more phosphate compared to other areas on the surface. When Ni²⁺ is added to the coating solution, the Al-Cu-Mg particle is more thickly coated compared to when the Ni²⁺ is not present. The slower rate of precipitation when Ni²⁺ is present in the coating solution increases the exposure of the alloy substrate to the acidic environment, so allowing more dissolution of Mg and Al from the Al-Cu-Mg particle. This results in the particle becoming more cathodic in nature, and therefore more coating deposits at this location. Evidence from SAM supports the presence of NiAl₂O₄, hypothesized in Part I, forming at coating pores later in the process.     

Laser-induced breakdown spectroscopy for on-line control of laser cleaning of sandstone and stained glass

Laser-induced breakdown spectroscopy (LIBS) was used to control the cleaning process of polluted sandstone and medieval stained glass. A combination of a KrF Excimer and LIBS was used to clean areas of the artwork. The spectroscopic study of the plasma emission was used to determine the elemental composition of the crust and the underlying material. The on-line implementation of the spectroscopic technique LIBS to the cleaning process provides important information about the optimal cleaning parameters of artworks from glass and stone in order to avoid over-cleaning. Received: 26 January 1999 / Accepted: 22 April 1999 / Published online: 7 July 1999     

The effect of cerium and lanthanum surface treatments on early stages of oxidation of A361 aluminium alloy at high temperature

X-ray photoelectron spectroscopy analysis has been used to study the surface of A361 aluminium alloy after electrodeposition of cerium and lanthanum compounds followed by oxidation tests in air at 100-500 °C for 2 h. Cerium and lanthanum oxide deposits are found on the β-AlFeSi second phase particles and to a lesser extent on the eutectic Al-Si areas, while the α-Al phase is covered with a thin aluminium oxide film. This uneven deposition may be related either to a preferential nucleation and growth process on active interfaces or to the differing electrical conductivity of the phases and intermetallic compounds of the alloy. Initial stages of oxidation of A361 alloy disclosed thickening of the aluminium oxide layer and Mg enrichment at the surface, especially above 400 °C. Rare earth deposits revealed two different effects: reduced Mg diffusion and enhanced thickening of the aluminium oxide film. A distinctive behaviour of Ce oxide appears at 300-500 °C related with Ce(III) to Ce(IV) transition.     

Microstructure and corrosion resistance of the layers formed on the surface of precipitation hardenable plastic mold steel by plasma-nitriding

Plasma-nitriding is used to improve the wear resistance and corrosion resistance of plastic mold steels by modifying the surface layers of these steels. In this study, a precipitation hardenable plastic mold steel (NAK80) was plasma-nitrided at 470, 500, and 530 °C for 4, 8, and 12 h under 25% N₂ + 75% H₂ atmosphere in an industrial nitriding facility. The microstructures of the base material and nitrided layers as well as the core hardness were examined, and various phases present were determined by X-ray diffraction. The corrosion behaviors were evaluated using anodic polarization tests and salt fog spray tests in 3.5% NaCl solution.The results had shown that plasma-nitriding does not cause the core to soften by overaging. Nitriding and aging could be achieved simultaneously in the same treatment cycle. Plasma-nitriding of NAK80 mold steel produced a nitrided layer composed of an outer compound layer constituting a mixture of ?-nitride and γ′-nitride and an adjacent nitrogen diffusion layer on the steel surface. The amount of ?-nitride and total nitrides increased with an increase in nitriding temperature and nitriding time. Corrosion study revealed that plasma-nitriding significantly improved the corrosion resistance in terms of corrosion potential, corrosion and pitting current density, and corrosion rate. This improvement was found to be directly related to the increase in the amount of ?-nitride at the surface, indicating the amount of ?-nitride controlling the corrosion resistance.     

A phase field method for simulating morphological evolution of vesicles in electric fields

A phase field method is developed to investigate the morphological evolution of a vesicle in an electric field, taking into account coupled mechanical and electric effects such as bending, osmotic pressure, surface tension, flexoelectricity, and dielectricity of the membrane. The energy of the system is formulated in terms of a continuous phase field variable and the electric potential. The governing equations of the phase field and the electric field are solved using the Galerkin weighted residual approach. The validation and robustness of the algorithm are verified by direct comparisons of the obtained numerical solutions with relevant experimental results. The morphological evolution of an axisymmetric vesicle under an electric field is studied in detail. The results demonstrate that the present method can simulate complex morphological evolutions of vesicles under coupled mechanical–electrical fields.     

A high-sensitivity in situ optical diagnostic technique for laser cleaning of transparent substrates

A differential optical transmission technique has been used to monitor in situ the efficiency of laser cleaning for the removal of sub-micrometer-sized particles on substrates transparent at the monitoring wavelength. This technique has been applied to the removal of sub-micrometer polystyrene particles on polyimide substrates using laser pulses of 30 ps duration at 292 nm while probing the material transmission at 633 nm. The sensitivity achieved -1/10⁴ for the transmission changes induced upon single-pulse laser exposure – allows us to monitor the removal of just a few sub-micron-sized particles from the probed region inside the irradiated area. Received: 2 October 2002 / Accepted: 7 October 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +33-3/87844082, E-mail: nchaoui@iut.univ-metz.fr RID="**" ID="**"Present address: Laboratoire de Chimie et Applications, Institut Universitaire de Technologie de Metz, Département Chimie, Rue Victor Demange, 57500 Saint-Avold, France