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The influence of $Ce^{3+}$ ions on the corrosion rate of stainless steel in acidic solutions of different pH-values
Aljana Petek, Sebastijan Kovačič, 2014, original scientific article

Abstract: The corrosion resistance of AISI 420 stainless steel in 0.1 mol $L^{−1}$ $H_2SO_4$ + 0.1 mol $L^{−1}$ $Na_2SO_4$ solutions at different pH-values and the inhibiting effect of $Ce^{3+}$ ions was studied using electrochemical polarization methods. The results reveal decreasing of the corrosion rate with an increasing the pH of the solution, which demonstrates the progressive protective character of the inhibitor used. At pH lower than 3.33, the corrosion inhibition was most probably a result of the competitive adsorption of $Ce^{3+}$ with $H^+$ ions on the cathodic sites of the electrode surface, and it was found to be dependent on the relative concentration of $H^+$/$Ce^{3+}$. The peroxide generated from the oxygen reduction reaction at pH 3.33 was found to be capable oxidize trivalent cerium (Ce) to the tetravalent state. As obtained hydroxide precipitates act as diffusion barrier hindering the corrosion processes, whereafter a spontaneous passivity occurs on the steel surface at this pH.
Keywords: acid corrosion, green corrosion inhibitor, stainless steel, electrochemical techniques
Published: 24.07.2017; Views: 590; Downloads: 251
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Modified surface of Cu, Zn, Cu10Zn and Cu40Zn with expression of hydrophobic properties for the purpose of corrosion protection
Gregor Žerjav, 2015, doctoral dissertation

Abstract: Copper and its alloys are soft and malleable metals and are often used for fabricating structures and monuments open to the atmosphere where they are subject to corrosion attack. There are many ways to protect metal against corrosion: corrosion inhibitors, protective layers, hydrophobic layers. He aim was to develop a simple technological process for forming hydrophobic, protective coatings for protection of Cu, Cu10Zn, Cu40Zn and Zn under conditions of atmospheric corrosion as tested in simulated urban rain. Carboxylic acids form self-assembled hydrophobic layers by adsorption to the positively charged metal surfaces via their carboxylic group. Corrosion inhibitors are often used to protect metals against corrosion in closed system. Most used corrosion inhibitors to protect Cu and its alloys is benzotriazole (BTAH) which showed good results in different environments. 2-mercaptobenzimidazole (2-MBI) is a derivative of BTAH with stronger affinity to adsorb on the Cu surface and showed good corrosion protection results in acidic solutions. Corrosion protection properties of the layers were tested with the use of electrochemical methods: potentiodynamic polarization and electrochemical impedance spectroscopy. The results were complement with immersion test where the weight loss was obtained. The properties of the layers were explored with surface-analytical methods: measurement of the contact angles, X-ray photoelectron spectroscopy, scanning electron microscopy with a chemical analysis and glow discharge optical emission spectroscopy. First the optimal conditions to produce hydrophobic coatings with the use of carboxylic acids were explored. The inhibition efficiency increased with increasing carbon chain length, longer preparation time in ethanol solution and increasing concentration of carboxylic acid. The inhibition of corrosion of Cu, Cu10Zn, Cu40Zn and Zn in simulated urban rain was further studied using the self-assembly of BTAH, 2-MBI and SA in ethanol solution, as individual inhibitors and in combinations. The morphology of layers differed greatly. The results of electrochemical measurements and weight loss immersion test ruled out BTAH as a possible inhibitor, unless combined with stearic acid. In the cases of Cu40Zn and Zn it even promoted corrosion. In contrast, 2-MBI gave good results, and even better in combination with stearic acid. SA layers provided the best long term corrosion protection of all tested inhibitors and exhibited the highest contact angles. 2-MBI provided less protection than SA. Combining organic inhibitor and stearic acid improves the corrosion protection properties of the self-assembled layers compare to individual layers. To make the procedure of layer preparation more appropriate for industrial application the time of immersion was decreased. Layers prepared on Cu with 1 min immersion time showed adequate corrosion protection of Cu in simulated urban rain. We also studied the possibility of combining SA with vitamin E in the layer preparation procedure. The modified layers formed with combination of Vitamin E and SA showed better corrosion inhibition properties for Cu and Cu40Zn in simulated urban rain as individual layers. Combining inhibitor and carboxylic acid together to prepare corrosion protective layers has a positive effect on the corrosion properties of the layers. Layers made combining corrosion inhibitor and carboxylic acid showed better corrosion protection than individual layers. The self-assembling process is a fast process shown by the tests made on the Cu layers with shorter immersion time. The addition of Vitamin E in the preparation of layers with carboxylic acids shows a positive effect on the corrosion properties of layers.
Keywords: copper, brass, corrosion, simulated urban rain, inhibitors, carboxylic acid, benzotriazole, 2-mercaptobenzimidazole
Published: 30.11.2015; Views: 929; Downloads: 105
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An effect of sodium dodecylsulfate on the corrosion of copper in sulphuric acid media
Regina Fuchs-Godec, Valter Doleček, 2004, original scientific article

Abstract: The effect of sodium dodecylsulfate (SDS) on copper corrosion in a solution of 0.5 M H2SO4 + x M SDS was studied using electrochemical polarisation measurements. The critical micelle concentration (CMC) of SDS in 0.5 M H2SO4 is 8 * 10-4 M, and the experimental concentrations of SDS were in the range below and above the CMC. It was found that SDS is a good anodic inhibitor at lower anodic overpotentials, i.e. very close to the rest potential. Adsorptionof the inhibitor obeys the Langmuir isotherm. Plots of log [▫$theta$▫/(1-▫$theta$▫)] versus log ▫$c_{inh}$▫ yielded straight lines with a slope change at the CMC. Accordingly, the CMC could be determined from these electrochemical measurements. The values of ▫$Delta$▫▫$G_{ads}$▫ calculated from the Langmuir plots are negative, suggesting that the inhibitive action of SDS in 0.5 M H2SO4 results from the electrostatic adsorption of C12H25SO4- ions onto the positively charged copper surface.
Keywords: electrochemistry, corrosion inhibitors, surfactants, potentiodynamic polarisation, corrosion kinetic parameters, copper, Langmuir isotherm, critical micelle concentration, sulphuric acid
Published: 01.06.2012; Views: 1204; Downloads: 87
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Inhibitory effect of non-ionic surfactants of the TRITON-X series on the corrosion of carbon steel in sulphuric acid
Regina Fuchs-Godec, 2007, original scientific article

Abstract: The corrosion inhibition characteristics of non-ionic surfactants of the TRITON-X series, known as TRITON-X-100 and TRITON-X-405, on stainless steel (SS) type X4Cr13 in sulphuric acid were investigated by potentiodynamic polarisation measurements. It was found that these surfactants act as good inhibitors of the corrosion of stainless steel in 2 mol L-1 H2SO4 solution, but the inhibition efficiency strongly depends on the electrode potential. Thepolarisation data showed that the non-ionic surfactants used in this study acted as mixed-type inhibitors and adsorb on the stainless steel surface, in agreement with the Flory-Huggins adsorption isotherm. Calculated Gads values are -57.79 kJ mol-1 for TRITON-X-100, and -87.5 kJ mol-1 for TRITON-X-405. From the molecular structure it can be supposed that these surfactants adsorb on the metal surface through two lone pairs of electrons on the oxygen atoms of the hydrophilic head group, suggesting a chemisorption mechanism.
Keywords: electrochemistry, corrosion inhibitors, non-ionic surfactants, Flory-Huggins isotherm, critical micelle concentration, sulphuric acid
Published: 01.06.2012; Views: 1403; Downloads: 84
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Effects of surfactants and their mixtures on inhibition of the corrosion process of ferritic stainless steel
Regina Fuchs-Godec, 2009, original scientific article

Abstract: The corrosion inhibition characteristics regarding mixtures of cationic/zwitterionic types of surfactant (Myristyltrimethylammonium bromide/Palmitylsulfo-betaineas), and non-ionic surfactant TRITON-X-405 mixed with 1 mM of KBr, as corrosion inhibitors for stainless steel (SS) (type X4Cr13) in aqueous solutions of 2 M H2SO4 were investigated using potentiodynamic polarisation measurements. The polarisation data showed that mixtures of the surfactants used in this study acted as mixed-type inhibitors, adsorbing on the stainless steel surface in agreement with the Flory-Huggins adsorption isotherm. The tensiometric results of this study suggest the existence of a second state of aggregation for zwitterionic/cationic surfactant mixtures. From these values of the free energy of adsorption, which in both mixtures decreased with respect to a single surfactant, we concluded that the adsorption in mixtures was stronger. The mixtures studied here showed good inhibition properties for ferritic stainless steel type X4Cr13 in 2 M H2SO4 solution.
Keywords: corrosion inhibitor, cationic surfactant, Zwitterionic surfactant, Flory-Huggins isotherm, Sulphuric acid
Published: 01.06.2012; Views: 1068; Downloads: 99
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Inhibition properties of TRITON-X-100 on ferritic stainless steel in sulphuricacid at increasing temperature
Regina Fuchs-Godec, Gregor Žerjav, 2009, original scientific article

Abstract: The inhibiting action of a non-ionic surfactant of the TRITON-X series (TRITON-X-100) on stainless steel type X4Cr13 in 1.0 M H2SO4 solution at five different temperatures was investigated by the potentiodynamic polarisation measurements. The inhibition efficiency has been calculated in the presence and in the absence of the inhibitor. The experimental data suggest that the inhibition efficiency increases with increasing concentration of the TRITON-X-100, and decreases with the increasing temperature. Adsorption of the non-ionic surfactant used here obeys the Flory- Huggins isotherm. The thermodynamic parameters, such as, the heat of adsorption, adsorption entropy, and the adsorption free energy, have been calculated by employing thermodynamic equations. Kinetic parameters, also been evaluated.
Keywords: non-ionic surfactants, corrosion inhibitors, sulphuric acid, Flory-Huggins adsorption isotherm
Published: 31.05.2012; Views: 1387; Downloads: 63
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The adsorption, CMC determination and corrosion inhibition of some N-alkyl quaternary ammonium salts on carbon steel surface in 2 M H2SO4
Regina Fuchs-Godec, 2006, original scientific article

Abstract: Electrochemical measurements were performed to investigate the effectiveness of cationic surfactants of the N-alkyl quaternary ammonium salt type, i.e. myristyltrimethylammonium chloride (MTACl), cetyldimethylbenzylammonium chloride (CDBACl), and trioctylmethylammonium chloride (TOMACl), as corrosion inhibitors for type X4Cr13 ferritic stainless steel in 2 M H2SO4 solution. Potentiodynamic polarization measurements showed that these surfactants hinder both anodic and cathodic processes, i.e. act as mixed-type inhibitors. It was found that the adsorption of the N-alkyl ammonium ion in 2 M H2SO4 solution follows the Langmuir adsorption isotherm. Plots of log ▫$[/theta$▫/(1-▫$/theta$▫)] versus log▫$c_{inh}$▫ yielded straight lines with a slope, which changed drasticallyat the critical micelle concentration (CMC) of the surfactants studied. Accordingly, the CMC could be accurately determined from these measurements. The calculated values of the free energy of adsorption ▫$/Delta$▫▫$G_{ads}$▫ are, in cases when the charge on the metal surface is negative with respect to the PZC, relatively high what is characteristically for the chemisorption. On the other hand, for positive metal surfaces it is assumed that ▫$SO_4^{2-}$▫ anions are adsorbed first, so the cationic species would be limited by the surface concentration of anions. Accordingly ▫$/Delta$▫▫$G_{ads}$▫ values were lower in this case and the adsorption is due to merely electrostatic attraction, which is characteristically of physisorption.
Keywords: electrochemistry, corrosion inhibitors, cationic surfactants, Langmuir isotherm, corrosion kinetic parameters, critical micelle concentration, sulphuric acid
Published: 30.05.2012; Views: 2013; Downloads: 86
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