Comparison of selected inhibitor doped sol–gel coating systems for protection of mild steel

Current legislation around the use of antifouling and anticorrosion coatings has increased the need to find an environment friendly alternative to existing biocide containing pretreatments for steel structures exposed to sea water. Sol–gel technology offers a solution to fouling and corrosion inhibition since sol–gel chemistry lends itself ideally to functionalisation with a variety of components, for example, corrosion inhibitors. In this study, we have utilised the above mentioned approach in order to produce an inhibitor doped sol–gel protective coating on mild steel. The corrosion protection performance of three inhibitors, i.e. SD (Shieldex303), MOLY (Moly-White101ED-PLUS) and ZAPP (Heucophos ZAPP), added individually to a sol–gel, and applied to mild steel Q panels, were evaluated using electrochemical impedance spectroscopy. The inhibitor containing coatings were shown to protect against corrosion of mild steel; the coatings containing the inhibitors Moly and ZAPP were the most effective of the systems tested.

Highlights

? Sol–gel coatings are potential candidate systems for the protection of mild steel substrates.

? Sol–gel chemistry allows a variety of corrosion inhibitors to be incorporated into the sol–gel coating matrix.

? Evaluation of corrosion inhibition efficiency of sol–gel coatings can be assessed using electrochemical impedance spectroscopy (EIS).     

Corrosion behavior of Cr electrodeposited from Cr(VI) and Cr(III)-baths using direct (DCD) and pulse electrodeposition (PED) techniques

A comparison was made between the electrochemical corrosion behaviors of chromium deposited from hexavalent [Cr(VI)] and trivalent [Cr(III)] chromium baths using direct current (DCD) and pulse electro deposited (PED) techniques. Chromium coatings were deposited on mild-steel (MS) substrate. The corrosion behavior of both DCD and PED chromium from Cr(VI) and Cr(III)-baths in 3.5%NaCl solution was studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results indicated that PED chromium from Cr(VI) and Cr(III)-baths have higher charge-transfer resistance R_ct and very low I_corr than that of DCD chromium on mild-steel substrate.     

Corrosion inhibition of mild steel by the new class of inhibitors [2,5-bis(n-pyridyl)-1,3,4-thiadiazoles] in acidic media

The inhibitor effect of 2,5-bis(n-pyridyl)-1,3,4-thiadiazoles (n-PTH) on the corrosion of mild steel in 1 M HCl and 0.5 M H₂SO₄ have been investigated using weight loss and electrochemical impedance spectroscopy. Results obtained reveal that these compounds are mixed-type inhibitors and behave better in 1 M HCl than in 0.5 M H₂SO₄. The adsorption of n-PTH on the mild steel surface in both acidic media follows a Langmuir isotherm model.     

双一[γ一（三乙氧基硅）丙基]四硫化物处理热镀铝锌层的耐蚀性研究

采用双-[γ-(三乙氧基硅)丙基]四硫化物(BTESPT)硅烷钝化液对热镀铝锌钢板进行了钝化处理.研究了在5%NaCl溶液中未钝化、硅烷钝化及铬酸盐钝化热镀铝锌钢板的极化曲线和电化学交流阻抗谱.通过中性盐雾试验比较了硅烷钝化膜与铬酸盐钝化膜的耐蚀性能.结果表明:经硅烷钝化液钝化后的热镀铝锌钢板,其腐蚀电位和电流密度下降,极化电阻增大,硅烷钝化膜抑制了热镀铝锌钢板的腐蚀过程,使得耐蚀性能远远高于铬酸盐钝化后的热镀铝锌钢板.     

Inhibition of mild steel corrosion in phosphoric acid solution by triazole derivatives

Corrosion inhibition by triazole derivatives (n-PAT) on mild steel in phosphoric acid (H₃PO₄) solutions has been investigated by weight loss and polarization methods. The results indicate that these compounds act as mixed-type inhibitors retarding the anodic and cathodic corrosion reactions with emphasis on the former and do not change the mechanism of either hydrogen evolution reaction or mild steel dissolution. Some kinetic parameters are obtained.     

Thermodynamic characterization of metal dissolution and inhibitor adsorption processes in mild steel/2,5-bis(n-thienyl)-1,3,4-thiadiazoles/hydrochloric acid system

The corrosion inhibition of mild steel in 1 M hydrochloric acid solution by some 2,5-bis(n-thienyl)-1,3,4-thiadiazoles (n-TTH) has been studied in relation to the concentration of the inhibitors as well as the temperature using chemical (weight loss) and electrochemical (ac impedance and dc polarisation) techniques. All the methods employed are in reasonable agreement. The protection efficiency increases with increasing inhibitors concentration and with increasing temperature. The thermodynamic functions of dissolution and adsorption processes were calculated from experimental polarisation data and the interpretation of the results are given. Adsorption of n-TTH was found to follow the Langmuir’s adsorption isotherm and the ability of the molecule to chemisorb on the steel surface was dependent on the position of the sulphur atom on the thienyl substituent.     

Anticorrosive properties with catalytic behaviour of primer PANI film and top PPy coating synthesised in presence of novel norephedrine based amino alcohol compound

Polyaniline film as primer coating was deposited on stainless steel (SS) in aniline containing aqueous oxalic acid solution, and subsequent synthesis of top PPy film with 2-((5-ethylthiophen-2-yl) methylamino)-1-phenylpropan-1-ol (AAN) compound of different concentrations was achieved in acetonitrile-LiClO₄ successfully. The corrosion performances of coated and uncoated electrodes in 3·5%NaCl solution were evaluated with the help of AC impedance spectroscopy, anodic polarisation plots and open circuit potential time curves. The protective effect of bilayer coatings with AAN compound on SS electrode grew in parallel with extended exposure time. The regular increase in the charge transfer resistance of SS/PANI/PPy-AAN17 electrode was attributed to allowing the limited ion diffusion of top PPy coating with AAN17 compound. The high 21764 Ω s^?1/2 value of the Warburg coefficient showed that PPy-AAN17 film on the SS/PANI coating led to the formation of protective oxide layers due to the catalytic behaviour of PANI film.     

Polyaniline coating on 304 stainless steel by electropolymerisation from aqueous NaOH solution for corrosion protection in NaCl medium

Abstract

Polyaniline (PAn) coating was electrochemically synthesised on 304 stainless steel using cyclic voltammetry in 0·25M NaOH solution containing 0·1M aniline. Characterisation of the adhesive and stable PAn coating was carried out by cyclic voltammetry, Fourier transform infrared spectroscopy and scanning electron microscopy. The protective properties of PAn coating on 304 stainless steel were elucidated using linear anodic potentiodynamic polarisation and Tafel test in 3·5%NaCl solution. Linear anodic potentiodynamic polarisation test results proved that the PAn coating improved the degree of protection against pitting corrosion in NaCl solutions. Tafel test results showed that the PAn coating appeared to enhance protection for 304 stainless steel in 3·5%NaCl solution.     

Lignin terpolymer for corrosion inhibition of mild steel in 10% hydrochloric acid medium

Lignin terpolymer has been obtained by grafting copolymerization of both dimethyl diallyl ammonium chloride (DMDAAC) and acrylamide (AM) onto lignin. The corrosion inhibition properties of the terpolymer were tested. The results showed that the highest corrosion inhibition percentage was over 95% in 10% HCl acid medium at 25 °C and 80 °C. The lignin terpolymer inhibitor adsorption followed Temkin isotherm at 25 °C and 80 °C, and the adsorption capability was in reverse proportion to the temperature according to −ΔG_ads. The effects of corrosion inhibition are the comprehensive synergistic effect through the graft reaction among lignin, AM and DMDAAC.     

Application of EIS and SEM to evaluate the influence of pigment shape and content in ZRP formulations on the corrosion prevention of naval steel

The effects of pigment volume concentration and morphology of zinc particles employed in the formulation of zinc rich paints (ZRP) suitable for the corrosion protection of naval steel in sea water, have been investigated using electrochemical impedance spectroscopy combined with open circuit potential measurements and SEM micrograph analysis. Different ZRP samples were tested during exposure to artificial sea water for up to 70 days. The characteristics and properties of the naval steel/ZRP coating/sea water systems were determined from an impedance transfer function model which involves the reactions occurring at the metal/ZRP and ZRP/solution interfaces as well as diffusion processes through the active ZRP coating. Information concerning the influence of concentration and shape of the zinc pigment on the corrosion protective behaviour of ZRP coatings and on the exposure time dependence of the system parameters allowed to interprete the form in which the galvanic action and the barrier effect diminish progressively. The degree of rusting of the steel substrates as well as the blistering resistance of the formulated ZRP have been also evaluated according to conventional ASTM standards.     

Poly(N-methyl pyrrole) and its copolymer with pyrrole for mild steel protection

In this study, it was aimed to overcome disadvantages of polypyrrole films like water up taking and resulting low stability, via copolymerization of pyrrole and N-methyl pyrrole and preparing their bilayer films. Poly(N-methyl pyrrole) coating was synthesized electrochemically on mild steel and its corrosion performance has been investigated in 3.5% NaCl aqueous solution, by using electrochemical impedance spectroscopy (EIS), anodic polarization curves and open circuit potential-time relation. This coating was found to have lower protection efficiency than single poly(pyrrole) coating. This case was related to weak adsorption behavior of poly(N-methyl pyrrole) film on mild steel. On the other hand, when this film was applied as a top coat on polypyrrole coated sample; the obtained coating system hindered the attack of corrosive environment and protected mild steel efficiently. The underlying poly(pyrrole) film was strongly adherent and the top poly(N-methyl pyrrole) coat improved barrier property by decreasing permeability and water mobility. Poly(pyrrole-co-N-methyl pyrrole) has also been synthesized from aqueous oxalic acid solutions containing various ratios of these two monomers. The copolymerization rate and protective behavior of copolymer were strongly affected by the monomer concentration ratio. The ratio of 1:3 (N-methyl pyrrole/pyrrole) gave the most protective copolymer coating and it exhibited better barrier property than single PPy. This was related to introduction of -CH₃ group which creates hydrophobic effect, when compared to -NH group of pyrrole unit. However, the solution with the ratio of 1:1 yielded a coating which had lower protection efficiency than single poly(pyrrole) film. This behavior was attributed to significant decrease in adsorption strength as the ratio of n-methyl pyrrole increased.     

On the corrosion inhibition of low carbon steel in concentrated sulphuric acid solutions. Part I: Chemical and electrochemical (AC and DC) studies

The influence of the concentration of adenine (AD), as a safe inhibitor, on the corrosion of low carbon steel (LCS) in aerated 4.0 M H₂SO₄ solutions was studied. The investigations involved weight loss, potentiodynamic polarization, impedance and electrochemical frequency modulation (EFM) methods. Variations of open-circuit potential (OCP) as a function of time till steady-state potentials were also studied. Measurements were conducted under the influence of various experimental conditions complemented with ex situ EDX examinations of the electrode surface. By using EFM measurements, corrosion current density was determined without prior knowledge of Tafel slopes. Results obtained revealed that together with iodide ion, AD is an effective corrosion inhibitor for LCS corrosion in H₂SO₄ solutions. Synergism between iodide ion and AD was proposed. Potentiodynamic polarization studies showed that AD alone and the mixture of AD and iodide ions act as mixed-type inhibitors for the corrosion of LCS in 4.0 M H₂SO₄ solution. The inhibition mechanism involves the electrostatic adsorption of protonated AD molecules on the LCS surface charged with a negative layer of chemisorbed I⁻ ions. An adherent layer of inhibitor is postulated to account for the protective effect. EDX examinations of the electrode surface confirmed the existence of such adherent layer on the electrode surface. The inhibition efficiency increases with increase in the concentration of AD and immersion time. The potential of zero charge (PZC) of the LCS electrode was determined in 4.0 M H₂SO₄ solutions in the absence and presence of 0.001 M KI, and the mechanism of adsorption was discussed. The results obtained from chemical and electrochemical measurements were in good agreement.     

2,5-Bis(4-dimethylaminophenyl)-1,3,4-oxadiazole and 2,5-bis(4-dimethylaminophenyl)-1,3,4-thiadiazole as corrosion inhibitors for mild steel in acidic media

2,5-Bis(4-dimethylaminophenyl)-1,3,4-oxadiazole (DAPO) and 2,5-bis(4-dimethylaminophenyl)-1,3,4-thiadiazole (DAPT) have been synthesised and their inhibiting action on the corrosion of mild steel in 1 M HCl and 0.5 M H₂SO₄ at 30 °C has been investigated by various corrosion monitoring techniques. At constant acid concentration, the inhibitor efficiency of both the compounds is found to increase with inhibitor concentration. DAPT is slightly more efficient in 0.5 M H₂SO₄ than in 1 M HCl whereas DAPO is more efficient in 1 M HCl. Of the two, DAPT appears to be a better inhibitor. Potentiostatic polarisation studies show that both are mixed-type inhibitors in 1 M HCl but cathodic-type in 0.5 M H₂SO₄. The inhibitors function through adsorption following Langmuir isotherm in both the acids. The electronic properties of DAPO and DAPT, obtained using the AM1 semi-empirical quantum chemical approach, have been correlated with their experimental inhibition efficiencies using the linear resistance model (LR). These inhibitors are considered as a non-cytotoxic substances.     

Evaluation of impedance measurements on mild steel corrosion in acid media in the presence of heterocyclic compounds

Five heterocyclic compounds, having a five atom ring, fused with the benzene ring (indole, benzimidazole, benzotriazole, benzothiazole and benzothiadiazole) were investigated as corrosion inhibitors of mild steel in 1 N HCl using impedance and polarisation resistance methods. Four of these compounds exhibit inhibition properties, while one of them, benzothiadiazole, stimulates the corrosion process. Adequate structure models of the interface are offered. The experimental data show a frequency distribution and therefore a modelling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. At high inhibitor concentrations a second time constant is observed in the impedance spectra. The values of the polarisation resistance determined by the polarisation resistance method are well correlated with the sum of the separate resistances from the impedance measurements.     

The inhibition of mild steel corrosion in acidic solutions by 2,5-bis(4-pyridyl)-1,3,4-thiadiazole: Structure-activity correlation

The effect of 2,5-bis(4-pyridyl)-1,3,4-thiadiazole (4-PTH) on the corrosion of mild steel in acidic media (1 M HCl, 0.5 M H₂SO₄, 1 M HClO₄) has been investigated using weight loss measurements, electrochemical impedance spectroscopy and potentiodynamic polarisation. These studies have shown that 2,5-bis(4-pyridyl)-1,3,4-thiadiazole is good inhibitor for mild steel in 1 M HCl, 0.5 M H₂SO₄ and 1 M HClO₄ solutions, the better performances are seen in the case of 1 M HCl solutions. But in 1 M HClO₄, the 4-PTH stimulates corrosion at low concentrations. Polarisation curves indicate that the 4-PTH is a mixed-type inhibitor in all acidic media and E (%) is temperature-dependent. Adsorption on the mild steel surface follows the Langmuir isotherm model in all acidic media. The electronic properties obtained using the Hartree-Fock AB initio 3-21G quantum chemical approach, were correlated with the experimental efficiencies.     

The effect of a DLC coating adhesion layer on the corrosion behavior of titanium and the Ti6Al4V alloy for dental implants

The properties of DLC layers provide for their broad use in medical applications. Their tribological properties are frequently utilized in big joint implants, and their barrier effect offers another benefit. The present work studied corrosion behavior of DLC coatings formed on titanium and Ti6Al4V alloy with a titanium or chromium inter-layer, in environments to which dental implants may be exposed. Electrochemical impedance spectroscopy, XPS surface analysis, ICP/MS chemical analysis method and a set of standard biological tests were employed in the study.     

Impedance and modulus analysis of the (Na0.6Ag0.4)2PbP2O7 compound

The electrical properties of the (Na_0.6Ag_0.4)₂PbP₂O₇ compound were studied using the complex impedance spectroscopy in the temperature range (502-667 K). Grain interior, grain boundary and electrode-material interface contributions to the electrical response are identified by the analysis of complex plan diagrams. The imaginary part of the modulus at several temperatures shows a double relaxation peaks, furthermore suggesting the presence of grains and grain boundaries in the sample. An analysis of the dielectric constants ?′, ?″ and loss tangent tan(δ) with frequency shows a distribution of relaxation times. The dc conductivity of the material is thermally activated with an activation energy about 0.8 eV which is in the vicinity of the that obtained from tan(δ) (E = 0.7 eV) and modulus (E_m = 0.68 eV) studies.     

Experimental and theoretical investigation of organic compounds as inhibitors for mild steel corrosion in sulfuric acid medium

Three synthesized organic compounds were tested as corrosion inhibitors for mild steel in sulfuric acid medium by potentiostatic polarization, FTIR spectroscopy and SEM techniques. Quantum chemical parameters were also calculated to characterize adsorption mechanism. Acceptable correlations were obtained between inhibition efficiency and the calculated quantum chemical parameters. It was found that the investigated compounds exhibit a good inhibition effect especially at 8-10 ppm range concentration, which makes them commercially important. The adsorption of inhibitors on the surface obeys Langmuir adsorption isotherm. The values of activation energy and the thermodynamic parameters, such as K_ads, , and were calculated.     

Validated numerical modelling of galvanic corrosion for couples: Magnesium alloy (AE44)-mild steel and AE44-aluminium alloy (AA6063) in brine solution

A numerical model is presented in this work that predicts the corrosion rate of a galvanic couple. The model is capable of tracking moving boundary of the corroding constituent of the couple. The corrosion rates obtained from the model are compared with those estimated from mixed potential theory and two experimental techniques, namely Scanning Vibrating Electrode Technique (SVET) and immersion technique. The corrosion rates predicted using the model are in good agreement with those estimated from the experimental techniques for magnesium alloy AE44-mild steel couple, however, the model under predicts the corrosion rate for AE44-aluminium alloy AA6063 couple.     

A diffuse phase transition study on Ba substituted (Na0.5Bi0.5)TiO3 ferroelectric ceramic

Polycrystalline perovskite lead free material (Na_0.5Bi_0.5)_0.91Ba_0.090TiO₃ was prepared by solid state reaction method. The crystal structure examined by X-ray powder diffraction indicates that the material was single phase with tetragonal structure. Dielectric studies exhibit a diffuse phase transition and characterized by a strong temperature and frequency dispersion of permittivity which relates cation disorder at A-site and exhibits relaxor behaviour. The dielectric relaxation has been modeled using the Vogel-Fulcher relationship, the calculated activation energy found to be E_a = 0.021 eV. Complex impedance analysis indicates the system undergoing a polydispersive non-Debye type relaxation. Also, used to characterize grain and grain-boundary resistivities of Ba substituted (Na_0.5Bi_0.5)TiO₃ ceramic. The phenomenon was also interpreted by accounting for microstructural differences. The corresponding relaxation times were also used to confirm the interpretation of complex impedance spectra. Overlapping of grain boundary and electrode relaxation processes can be separated above about 4000 C. Electrical modulus spectroscopy studies have been performed. The conductivity parameters such as ion-hopping rate (ω_p) and the charge carrier concentration (K¹) have been calculated using Almond and West formalism.