Corrosion inhibition of aluminum in 1 M H3PO4 solutions by ethanolamines

The inhibitive effect of the investigated compounds (ethanolamine (I), diethanolamine (II) and triethanolamine (III)) on the corrosion behavior of aluminum in 1 M H₃PO₄ solution using weight loss, galvanostatic polarization and quantum chemical calculation methods was studied. The inhibition efficiency was found to depend on type and concentration of the additives and also on temperature. The effect of addition of halide ions to various concentrations of these compounds has also been studied. The apparent activation energy (E_a) and other thermodynamic parameters for the corrosion process have also been calculated and discussed. The galvanostatic polarization data indicated that these inhibitors were of mixed-type. The slopes of the cathodic and anodic Tafel lines (β_c and β_a) are approximately constant and independent of the inhibitor concentration. The adsorption of these compounds on aluminum surface has been found to obey the Freundlich adsorption isotherm. Some quantum chemical parameters and Mulliken charge densities for investigated compounds were calculated by the AM1 semi-empirical method to provide further insight into the mechanism of inhibition of the corrosion process. The theoretical results are then compared with experimental data.     

Pitting of Al and Al–Si alloys in KSCN solutions and the effect of light

The pitting corrosion susceptibility of pure Al and three Al-Si alloys, namely (Al-6%Si), (Al-12%Si) and (Al-18%Si) has been studied in 0.04 M KSCN solution. Measurements were carried out under the effect of various experimental conditions using cyclic polarization, potentiostatic and galvanostatic techniques. In all cases, the potentiodynamic anodic polarization curves do not exhibit active dissolution region due to spontaneous passivation. The passivity is due to the presence of a thin film of Al₂O₃ on the anode surface. The passive region is followed by pitting corrosion, at a certain critical potential, pitting potential (E_pit), as a result of breakdown of the passive film by SCN^? anions. Cyclic polarization measurements allowed the determination of the pitting corrosion parameters, namely the pitting potential and the repassivation potential (E_rp). Alloyed Si decreased the passive current (j_pass) and shifted both E_pit and E_rp towards more positive values. Thus alloyed Si suppressed pitting attack. The effect of illumination on passivity and the initiation of pitting corrosion on Al in KSCN solutions was also studied. It is observed that illumination of Al leads to an increase in its pitting corrosion resistance-apparent from j_pass, E_pit, and E_rp measurements in aggressive KSCN solutions.     

On the corrosion inhibition of iron in hydrochloric acid solutions,Part I: Electrochemical DC and AC studies

The inhibitive action of 4-methyl pyrazole (4MP) against the corrosion of iron (99.9999%) in solutions of hydrochloric acid has been studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). At inhibitor concentration range (10^?3–10^?2 M) in 1.0 M acid, the results showed that 4MP suppressed mainly the anodic processes of iron corrosion in 1.0 M HCl by adsorption on the iron surface according to Temkin adsorption isotherm. Both potentiodynamic and EIS measurements reveal that 4MP inhibits the iron corrosion in 1.0 M HCl and that the efficiency increases with increasing inhibitor concentration. Data obtained from EIS were analyzed to model the corrosion inhibition process through an equivalent circuit.     

Xanthione: A new and effective corrosion inhibitor for mild steel in sulphuric acid solution

The adsorption and inhibition effect of xanthione (XION) on mild steel in 0.5 M H₂SO₄ at 303–333 K were studied using gravimetric and UV–visible spectrophotometric methods. The results obtained show that XION acts as an effective corrosion inhibitor for mild steel in sulphuric acid and inhibition efficiency reaches 98.0% at a very low inhibitor concentration of 10 μM. Inhibition efficiency was found to increase with increase in XION concentration but decreased with temperature suggesting physical adsorption mechanism. Arrhenius law and its transition equation lead to estimate the activation parameters of the corrosion process. XION inhibits the corrosion of mild steel effectively at moderate temperature and adsorbs according to the Langmuir isotherm. Thermodynamic parameters governing the adsorption process have been calculated and discussed. The UV–visible absorption spectra of the solution containing the inhibitor after the immersion of mild steel specimen indicate the formation of a XEN–Fe complex. Attempt to correlate the molecular structure to quantum chemical indices was made using density functional theory (DFT).     

Pitting Corrosion Mechanisms and Characteristics of Aluminum in Solar Heating Systems

The complex characteristics and mechanisms of aluminum pitting corrosion in a solar heating system were studied by the chemical immersion method and electrochemical techniques as well as fractal theory. The results showed that pitting corrosion of Al occurred in a tap water environment due to the local enrichment of Cl^? ions. The higher the Cl^? ions concentration, the more negative the critical pitting potential (E_b) of Al. A linear relationship between E_b and the logarithm of Cl^? ions concentration was observed. The pitting corrosion mechanism of Al in neutral water was explained in terms of complexation corrosion theory. The corrosion surface images of aluminum immersed in tap water were captured and analyzed by image processing technique and box‐dimension method. The fractal characteristics of pit distribution, described by fractal dimension, have been identified. The fractal dimension of the pit distribution increased with the increase of immersion time and had the same trend as that of the weight loss. Fractal dimension can, thus, be used as an important parameter for quantitative evaluation of pitting corrosion of aluminum.     

Inhibition of cold rolled steel corrosion in sulphuric acid solution by 2-mercapto-1-methylimidazole: Time and temperature effects treatments

2-Mercapto-1-methylimidazole (MMI) has been evaluated as a corrosion inhibitor for cold rolled steel in aerated 2 M H₂SO₄ by gravimetric method. The effect of MMI on the corrosion rate was determined at various immersions time and concentrations. The effect of the temperature on the corrosion behaviour with addition of different concentrations of MMI was studied in the temperature range 30–60 °C. The MMI acts as an effective corrosion inhibitor for cold rolled in sulphuric acid medium. The inhibition process is attributed to the formation of an adsorbed film of MMI on the metal surface which protects the metal against corrosion. The protection efficiency increased with increase in inhibitor concentration at various immersions time and decreased with increase in temperature. Adsorption of MMI on the cold rolled steel surface is found to obey the Langmuir adsorption isotherm. Some thermodynamic functions of dissolution and adsorption processes were also determined.     

Polyvinyl alcohol–sulphanilic acid water soluble composite as corrosion inhibitor for mild steel in hydrochloric acid medium

The inhibitive action of synthesised polyvinyl alcohol–sulphanilic acid (PVASA) composite on the corrosion of commercial mild steel in 1 M HCl medium has been investigated by weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopic (EIS) methods. Characterization of PVASA composite has been carried out using Fourier transform infrared spectroscopy (FTIR). Experimental results reveal that PVASA composite acts as an inhibitor in the acid environment. The inhibition efficiency increases with an increase in the concentration of the inhibitor. Maximum inhibition efficiency of PVASA composite was found to be 84% at 6000 ppm. Thermodynamic and kinetic parameters have been obtained from temperature studies. Electrochemical measurement reveals that PVASA composite acts as a mixed inhibitor and the adsorption follows Langmuir adsorption isotherm.     

Poly (vinyl alcohol – aniline) water soluble composite as corrosion inhibitor for mild steel in 1 M HCl

Poly (vinyl alcohol – aniline) PVAA composite was tested for its performance in protecting mild steel MS against corrosion in 1 M HCl. The inhibitive parameters were evaluated by means of weight loss, electrochemical polarization and impedance methods. Results indicated that the addition of PVAA to the acid reduces the corrosion of the metal. Inhibition efficiency increases with increase in inhibitor concentration. The results further revealed that PVAA at a concentration of 2000 ppm furnishes a maximum of 92% inhibition efficiency. Thermodynamic parameters such as free energy of adsorption, heat of adsorption, etc., had been evaluated from temperature studies. The adsorption of PVAA followed Langmuir and Temkin adsorption isotherms. Polarization curves revealed that PVAA is a mixed inhibitor.     

Three dimensional micromachining on aluminum surface by electrochemical wet stamping technique

We proposed an up–down working mode of electrochemical wet stamping technique (EC-WETS) for three dimensional (3D) micromachining on aluminum (Al) surface. 3D microstructures on a Si mold were transferred on to an agarose hydrogel containing 15% NaNO₃, 2% MgF₂, 1% NaOH and 5% glycerin, which acted as the quasi-solid electrolyte for the electrochemical micromachining. The transferred 3D microstructures on agarose hydrogel were then duplicated onto Al surface through anodic dissolution. The micromachining quality was improved by pulse-potential method dramatically with a machining tolerance lower than 200 nm and an average removal rate of 210 nm min^− 1 in the Z direction. This method was proved to be a highly efficient, low cost and green method for 3D micromachining on active metal surface, which would be valuable for the manufacture of microelectromechanical system (MEMS).     

Electrodeposition of aluminum on magnesium alloy in aluminum chloride (AlCl3)–1-ethyl-3-methylimidazolium chloride (EMIC) ionic liquid and its corrosion behavior

A dense and adhesive Al layer was successfully electrodeposited on a Mg alloy in aluminum chloride–1-ethyl-3-methylimidazolium chloride ionic liquid. The corrosion resistance of the uncoated and Al-coated samples was evaluated by electrochemical impedance spectroscopy and potentiodynamic polarization measurements in 3.5 wt% NaCl solution. It was confirmed that the protective Al layer significantly reduces the corrosion rate of the Mg alloy. However, the deposition potential was a crucial factor that governed the structure and therefore the protection capability of the Al layer.     

Microstructural and Mechanical Properties of Al-20%Si Containing Cerium

In this paper the effect of cerium addition in hypereutectic Al-Si alloys was studied. Casting method was used to produce Al-20Si with variation of Ce contents. The sample characterization studied was investigated by Optical Microscope, X-ray fluorescence and X-ray Diffraction. Vickers microhardness and wear test was carried out to study the influence of Ce towards the Al-20Si alloys. The addition of Ce in the Al-20Si alloys refined the Si primary phase as the Ce content increases. The results showed that the addition of 0.46 to 2.24 wt.% of cerium in Al-20Si alloys led to the formation of fine cells dispersed in the Al-matrix. These fine cells consist of a mixture of eutectic Si particles and intermetallic Al3Ce and CeAl1.2Si0.8 phase in Al matrix. The amount of rod- like intermetallic Al3Ce and CeAl1.2Si0.8 phase increases with increasing Ce content. The microhardness of Al-20Si alloys increases with the increase in Ce content. Addition of Ce up to 1.61 wt.% Ce improve the wear properties of Al-20Si alloy.     

Study of complex formation in Al(III) – Gluconic acid system and the influence of UV light on the dissolution and passive behavior of Al

The passive and dissolution behavior of Al was studied in 0.25 M gluconic acid solution (HG) under the conditions of continuous illumination (300–400 nm) and non-illumination at 25 °C. Measurements were conducted based on cyclic polarization technique, complemented with SEM examinations. Addition of HG induced localized attack, rather than anodizing, via the formation of Al–gluconate soluble complex species. Complexation with gluconate (G^?) anion was elucidated using elemental analysis, IR-spectroscopy and UV–vis spectra. The infrared spectral data is in agreement with coordination through carboxylate-to-metal, with G^? acting as a monodentate ligand. A little ennoblement in the pitting potential (E_pit) was observed for the illuminated electrode (little influence on pit nucleation). On the other hand, the anodic currents at potentials exceeding the pitting potential are greatly reduced upon illumination (significant influence on pit growth and propagation). These findings indicated that the incident photons of the UV light enhanced the resistance of the passive film towards localized attack. These explained in terms of a photo-induced modification of the passive film formed on the anode surface, which render it more resistant to the onset of attack. The repassivation potential (E_rp), however, was found to be independent of the energy of the incident UV light. SEM images revealed that the severity of localized attack was suppressed upon illumination.     

Inhibitive action of ethanol extracts from Nauclea latifolia on the corrosion of mild steel in H2SO4 solutions and their adsorption characteristics

The inhibitive action of ethanol extracts from leaves (LV), bark (BK) and roots (RT) of Nauclea latifolia on mild steel corrosion in H₂SO₄ solutions at 30–60 °C was studied using weight loss and gasometric techniques. The extracts were found to inhibit the corrosion of mild steel in H₂SO₄ solutions and the inhibition efficiencies of the extracts follow the trend: RT > LV > BK. The inhibition efficiency increased with the extracts concentration but decreased with temperature rise. Physical adsorption of the phytochemical components of the plant on the metal surface is proposed as the mechanism of inhibition. The adsorption characteristics of the inhibitor were approximated by the thermodynamic-kinetic model of El-Awady et al.     

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.     

Corrosion inhibition of carbon steel immersed in a 1 M HCl solution using benzothiazole derivatives

Corrosion inhibition effect of 2-mercaptobenzothiazole (MBT) and 2-aminobenzothiazole (ABT) compounds on ST-37 carbon steel in 1 M hydrochloric acid solution was investigated by electrochemical impedance spectroscopy (EIS), and it was observed that both of these compounds have corrosion inhibition effect on carbon steel. Evaluation of electrochemical behavior in test solutions showed that by increasing the immersion time from 15 to 300 min, corrosion resistance of samples is increased and at the same immersion time MBT has a better corrosion inhibition in comparison to ABT. AFM technique was performed for MBT and ABT. The results of calculations showed superior inhibition efficiency of MBT in comparison to ABT. This can cause easier protonation and consequently adsorption on the metal surface occurs.     

The inhibition mechanism of pitting corrosion of pure aluminum by nitrate and sulfate ions in neutral chloride solution

The inhibition mechanism of pitting corrosion of natural oxide film-covered pure aluminum by NO⁻ ₃ and SO²⁻ ₄ ions has been examined in 0.1 M NaCl solution using potentiodynamic polarization experiments, a.c. impedance spectroscopy, Auger electron spectroscopy and a combination of the potentiostatic current transient method and optical microscopy. It was found that NO⁻ ₃ ions can be incorporated into the natural oxide film on pure aluminum at open-circuit potential, but the incorporation of SO²⁻ ₄ ions into the film hardly occurs. The incorporation of NO⁻ ₃ ions lowered the pitting susceptibility of pure aluminum in 0.1 M NaCl solution. Based upon the experimental results, it is suggested that the pitting corrosion inhibition mechanism by anions can be classified into two different groups: inhibition by competitive adsorption of anions (SO²⁻ ₄) with Cl⁻ ions and inhibition by the incorporation of anions (NO⁻ ₃) into the film rather than competitive adsorption. Both cases may impede the incorporation of Cl⁻ ions into the film, thus inhibiting pitting corrosion of natural oxide film-covered pure aluminum in chloride solutions. Received: 16 October 1998 / Accepted: 6 January 1999     

Adsorption of benzene from benzene/n-C6 and n-C7 mixture by nano Beta zeolite with different Si/Al ratios

The adsorption of benzene from benzene/n-alkane mixtures was studied by two types of nano Beta zeolite with Si/Al ratios of 11.5 and 24.5. Benzene was adsorbed into benzene/n-hexane and n-heptane mixtures which had 0.5% up to 10% mole fraction of benzene using batch technique in the ambient temperature. The nano Beta zeolite has active sites on its surface, which have interaction with π electron in benzene, and this can increase the heat of adsorption. The Si/Al ratio defines the number of active sites in the zeolite surface and the heat of adsorption. However, an increase in the active sites of Beta zeolite declines the entropy of adsorption. Therefore, free energy of mixing specifies the potential of adsorption in Beta zeolite.As the results indicated in all mixtures, benzene is adsorbed more than n-hexane and n-heptane into the Beta zeolite surface, which suggests that this type of zeolite has a high separation factor (∼50) for benzene in Beta zeolite (Si/Al = 24.5). Also, Beta zeolite with Si/Al = 24.5 had a greater separation factor than Beta zeolite with Si/Al = 11.5 in similar mixtures.     

The protectivity of aluminum and its alloys with transition metals

The mechanism of the protectivity of aluminum and supersaturated aluminum alloys containing W, Mo, Ta and Cu has been investigated in chloride environments. The potential of zero charge (PZC) of the passive film was evaluated by a method based on impedance spectroscopy. The chloride ion adsorption on the passive film was measured by means of an in situ radiotracer technique. Constituents of the passive film as a function of depth were investigated by means of ex situ spectroscopic techniques including XPS, ISS and SIMS. The PZCs of the passive films of Al and Al alloys were calculated from the flatband potentials. A linear correlation between pitting potential and the PZC was found. Adsorption of the chloride ion on the Al-Ta surface starts at more anodic potentials than those of pure Al, and this shift is in agreement with the anodic shift of the PZC. A constant surface concentration of chloride ion was observed during the induction time for breakdown. A significant de crease of OH⁻ concentration in the passive film of Al and its alloys has been found after the passive film has undergone breakdown. The mole fraction of the alloying elements in the surface region of the passive film is ca. 1–8%. The adsorption of the chloride ion on the surface of the passive film is influenced by the anodic PZC shift, which varies with the alloying element. However, retardation of the chloride penetration into the passive film by blocking of the entry site by oxide ions of the alloying element controls the rate of breakdown. Received: 18 November 1996 / Accepted: 17 February 1996     

Synergistic inhibition effects between leaves and stem extracts of Sida acuta and iodide ion for mild steel corrosion in 1 M H2SO4 solutions

The synergistic action caused by iodide ions on the corrosion inhibition of mild steel in 1 M H₂SO₄ by leaves and stem extracts of Sida acuta was studied using weight loss and hydrogen evolution methods at 30–60 °C. It was found that the leaves and stem extracts of S. acuta inhibited the acid induced corrosion of mild steel. Addition of iodide ions enhances the inhibition efficiency to a considerable extent. The inhibition efficiency increases with increase in the iodide ion concentration but decreases with rise in temperature. Adsorption of the extracts alone and in combination of iodide ion was found to obey Freundlich adsorption isotherm at all temperatures studied. Inhibition mechanism is deduced from the temperature dependence of the inhibition efficiency as well as from assessment of kinetic and activation parameters that govern the processes. The synergism parameter (S₁) is defined and evaluated from the inhibition efficiency values. This parameter for the different concentrations of iodide ions from the two techniques employed is found to be greater than unity indicating that the enhanced inhibition efficiency of the extracts caused by the addition of iodide ions is due to synergism.