Analysis of the electrochemical reaction behavior of alloy AZ91 by EIS technique in H3PO4/KOH buffered K2SO4 solutions

The EIS technique was used to analyze the electrochemical reaction behavior of Alloy AZ91 in H₃PO₄/KOH buffered K₂SO₄ solution at pH 7. The corrosion resistance of Alloy AZ91 was directly related with the stability of Al₂O₃ · xH₂O rich part of the composite oxide/hydroxide layer on the alloy surface. The break down of the oxide layer was estimated to occur mainly on the matrix solid solution phase in Alloy AZ91. The mf capacitive loop arose from the relaxation of mass transport in the solid oxide phase in the presence of Al₂O₃ · xH₂O rich part and from Mg⁺ ion concentration within the broken area in the absence of Al₂O₃ · xH₂O rich part in the composite oxide structure on the alloy surface. The lf inductive loop had tendency of disappear when the dissolution rate of the alloy decreased as a result of the formation of the protective oxide layer.     

Tribocorrosion of 316L stainless steel and TA6V4 alloy in H2SO4 media

Tribocorrosion of stainless steel 316L and titanium alloy TA6V4 has been conducted in a sulphuric acid solution using an apparatus designed and built for evaluating the joint action of corrosion and wear. The material electrochemical and wear behaviours have been investigated during friction tests under electrochemical potential control. The specimens have been submitted to friction against an alumina ball under cathodic, free and anodic potentials. The friction coefficient, the wear rate and the current density were measured and the obtained results were discussed in terms of passivating film stability and repassivation kinetics.     

Corrosion behaviour of cermet-based coatings with a bond coat in 0.5 M H2SO4

The corrosion behaviour of an HVOF Ni–5Al/WC–17Co coating on Al-7075 is investigated in 0.5 M H₂SO₄. In the temperature range of 25–45 °C, the coating exhibits pseudopassivity that effectively protects from localized corrosion. At 25 °C, pseudopassivity proceeds via three stages: during the first stage, oxidation of W in the binder phase occurs. The second stage is characterized by oxidation of W in both the binder and the carbide particles. The third stage is characterized by intensive hydration of WO₃ and formation of Co₃O₄. During the second and third pseudopassive stages, the formation of a bi-layer surface film is postulated. The inner layer, consisting of anhydrous oxides, has a barrier character. The outer layer, composed of WO₃ · xH₂O, is unstable. In case of surface film disruption, the bond coat successfully hinders corrosion propagation into the Al-alloy. Higher electrolyte temperatures lead to faster corrosion kinetics and higher tendency for pitting.     

Electrochemical study of corrosion inhibition and adsorption behaviour for pure iron by polyacrylamide in H2SO4: Synergistic effect of iodide ions

Corrosion inhibition and adsorption behaviour for pure iron in 0.5 M H₂SO₄ by polyacrylamide (PA) were investigated using electrochemical techniques. The effect of iodide ion additives was also studied. It was found that inhibition efficiency increased with PA concentration. Corrosion inhibition was afforded by adsorption of PA onto the metal following El-Awady kinetic-thermodynamic adsorption isotherm model via chemisorption mechanism. A mixed inhibition mechanism is proposed for the inhibitive effects of PA as revealed by potentiodynamic polarization technique. A synergistic effect was observed between PA and KI as evident from the values of synergism parameter found to be greater than unity.     

Copper corrosion inhibition in O2-saturated H2SO4 solutions

Corrosion inhibition of copper in O₂-saturated 0.50 M H₂SO₄ solutions by four selected amino acids, namely glycine (Gly), alanine (Ala), valine (Val), or tyrosine (Tyr), was studied using Tafel polarization, linear polarization, impedance, and electrochemical frequency modulation (EFM) at 30 °C. Protection efficiencies of almost 98% and 91% were obtained with 50 mM Tyr and Gly, respectively. On the other hand, Ala and Val reached only about 75%. Corrosion rates determined by the Tafel extrapolation method were in good agreement with those obtained by EFM and an independent chemical (i.e., non-electrochemical) method. The chemical method of confirmation of the corrosion rates involved determination of the dissolved Cu²⁺, using ICP-AES (inductively coupled plasma atomic emission spectrometry) method of chemical analysis. Nyquist plots exhibited a high frequency depressed semicircle followed by a straight line portion (Warburg diffusion tail) in the low-frequency region. The impedance data were interpreted according to two suitable equivalent circuits. The kinetics of dissolved O₂ reduction and hydrogen evolution reactions on copper surface were also studied in O₂-saturated 0.50 M H₂SO₄ solutions using polarization measurements combined with the rotating disc electrode (RDE). The Koutecky-Levich plot indicated that the dissolved O₂ reduction at the copper electrode was an apparent 4-electron process.     

Kinetics of H2O2 reaction with oxide films on carbon steel

The nature of carbon steel surfaces in 0.01 M borate solutions (pH 10.6) have been characterized using a range of electrochemical techniques and ex situ analyses such as Raman and Auger spectroscopy. Their subsequent behaviour on exposure to 10⁻³ M H₂O₂-containing solutions has also been studied. The anodically oxidized carbon steel surfaces have been characterized according to three regions: (I) the potential range <−0.5 V (vs SCE), when the surface is active and covered by Fe^II/Fe^III oxide/hydroxide; (II) the potential range −0.5 V to 0.0 V when the surface is passivated by an outer layer of Fe^III oxide/hydroxide over the inner layer of Fe^II/Fe^III oxide/hydroxide; and (III) potentials >0 V when further growth of the underlying layer appears to lead to minor film breakdown/restructuring. The addition of H₂O₂ to films grown in the passive region or above (II and III) leads initially to a degradation of the outer layer allowing increased growth of the inner layer. Subsequently, the outer passivating layer is repaired and passivity re-established. These changes appear to be confirmed by Raman spectroscopy.     

Synergistic effect of iodide ion and polyacrylic acid on corrosion inhibition of iron in H2SO4 investigated by electrochemical techniques

Corrosion inhibition of iron in H₂SO₄ by polyacrylic acid (PAA) was investigated using electrochemical techniques at 30 °C. Results obtained indicate that PAA inhibited the corrosion of iron in the acid medium. Inhibition efficiency increases with increase in PAA concentration and synergistically enhanced on addition of iodide ions. Potentiodynamic polarization results suggest that PAA functions as a modest cathodic inhibitor. The adsorption of PAA onto the iron surface followed Temkin adsorption isotherm. FTIR analysis revealed that the synergistic effect due to co-adsorption of iodide ions and PAA is co-operative in nature.     

Tuning DOS measuring parameters based on double-loop EPR in H2SO4 containing KSCN by Taguchi method

In the present work, a higher resolution than that of standard DL-EPR technique was obtained by tuning the degree of sensitisation (DOS) measuring parameters. SS304 with different sensitisation conditions was chosen. Acid and depassivator concentration, temperature, scan rate and reverse potential were defined as key factors and Taguchi was applied. The optimal condition was found to be 1 M H₂SO₄, 0.02 M KSCN, 40 °C, 30 mV/min scan rate and 200 mV reverse potential. Main factors were acid concentration, scan rate, depassivator concentration. An increase in DOS from 18 to 42.2 in the 60 min sensitised sample was observed.     

Corrosion behavior of Cr/Cu-coated Mg alloy (AZ91D) in 0.1 M H2SO4 with different concentrations of NaCl

An electroplating process was proposed for obtaining a protective Cr/Cu deposit on the two-phase Mg alloy AZ91D. The corrosion behavior of Cu-covered and Cr/Cu-covered AZ91D specimens was studied electrochemically in 0.1 M H₂SO₄ with different NaCl concentrations. Experimental results showed that the corrosion resistance of an AZ91D specimen improved significantly after Cr/Cu electrodeposition. The corrosion resistance of Cr/Cu-covered AZ91D decreased with increasing NaCl concentration in 0.1 M H₂SO₄ solution. After immersion in a 0.1 M H₂SO₄ with a NaCl-content above 3.5 wt.%, the surface of Cr/Cu-covered AZ91D suffered a few blisters. Cracks through the Cr deposit provided active pathways for corrosion of the Cu and the AZ91D substrate. Formation of blisters on the Cr/Cu-covered AZ91D surface was confirmed based on the results of an open-circuit potential test, which detected an obvious potential drop from noble to active potentials.     

Inhibition effect of 6-benzylaminopurine on the corrosion of cold rolled steel in H2SO4 solution

The inhibition effect of 6-benzylaminopurine (BAP) on the corrosion of cold rolled steel (CRS) in 1.0-7.0 M H₂SO₄ at 25-50 °C was studied by weight loss and potentiodynamic polarization methods. Fourier transform infrared spectroscopy (FTIR) and atomic force microscope (AFM) were used to characterize the CRS surface. The results showed that BAP was a good inhibitor in 1.0 M H₂SO₄, and the adsorption of BAP obeyed the Temkin adsorption isotherm. Polarization curves showed that BAP acted as a mixed-type inhibitor in sulfuric acid. Depending on the results, the inhibitive mechanism was proposed.     

Corrosion evaluation and surface characterization of the corrosion product layer formed on Cu-6Sn bronze in aqueous Na2SO4 solution

The binary bronze alloy Cu-6Sn corrosion, and formation and properties of corrosion product layer (patinas) during 12 days of exposure to 15 mM Na₂SO₄ aqueous solution were investigated by a range of diverse experimental techniques. For the reasons of comparison, some techniques were applied, in parallel, to copper. Gravimetric measurements revealed lower corrosion rates of bronze than those of copper, probably caused by the presence of tin compounds in the corrosion product layer. Cyclic voltammetry results showed that the oxidation processes on bronze are affected by the formation of tin oxide species. Electrochemical impedance spectroscopy showed that, as opposed to copper which produced only two time constants, bronze corrosion resistance was dominated by the additional high-frequency time constant representing redox processes occurring at the corrosion product surface. SEM, ATR FTIR and PIXE results suggest that Cu-6Sn bronze corrosion in 15 mM Na₂SO₄ solution was impeded by the formation of two-layered structure of corrosion products that formed due to selective dissolution of copper at the layer/solution interface, leaving the outer layer enriched in highly corrosion resistant Sn oxi/hydrohide species.     

Inhibition of copper corrosion by isatin in aerated 0.5 M H2SO4

The corrosion inhibition of commercial copper by means of isatin was studied in aerated 0.5 M H₂SO₄ in the temperature range 25-55 °C using weight-loss, potentiodynamic and spectrophotometric tests, and determination of double layer capacitance. Inhibition efficiencies up to 94% in the concentration range of 1×10⁻⁴-7.5×10⁻³ M of isatin were obtained. The corrosion rates estimated with weight-loss measurements were higher than those correspondingly determined with the potentiodynamic test, especially at higher concentrations of inhibitor. This is in accord with other researches that have pointed out the limitation of the Tafel line extrapolation method in the determination of corrosion rates. The kinetics of cuprous and cupric ion formation and UV-visible spectra support the formation hypothesis of a complex between copper and isatin. The adsorptive behaviour of isatin on copper 0.5 M H₂SO₄ was also investigated.     

Three pyrazine derivatives as corrosion inhibitors for steel in 1.0 M H2SO4 solution

The inhibition effect of three pyrazine derivatives of 2-methylpyrazine (MP), 2-aminopyrazine (AP) and 2-amino-5-bromopyrazine (ABP) on the corrosion of cold rolled steel (CRS) in 1.0 M H₂SO₄ solution was studied by weight loss, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) methods. The results show that all pyrazine compounds are good inhibitors, and inhibition efficiency follows the order: ABP > AP > MP. The adsorption of each inhibitor on CRS surface obeys Langmuir adsorption isotherm. For all these pyrazine derivatives, they act as mixed-type inhibitors. The probable inhibitive mechanism is proposed from the viewpoint of adsorption theory.     

Synergism between red tetrazolium and uracil on the corrosion of cold rolled steel in H2SO4 solution

The synergism between red tetrazolium (RT) and uracil (Ur) on the corrosion of cold rolled steel (CRS) in H₂SO₄ solution is first investigated by weight loss, potentiodynamic polarization, and atomic force microscope (AFM). Effects of inhibitor concentration (25-500 mg l⁻¹), temperature (20-50 °C), and acid concentration (1.0-5.0 M) on synergism are discussed systematically. The results reveal that RT has a moderate inhibitive effect, and its adsorption obeys the Freundlich adsorption isotherm. For Ur, it has a poor effect. However, incorporation of RT with Ur significantly improves the inhibition performance, and produces synergistic inhibition effect.     

Investigation of the inhibition effect of indole-3-carboxylic acid on the copper corrosion in 0.5 M H2SO4

Inhibition of the copper corrosion by means of indole-3-carboxylic acid (ICA), was studied in 0.5 M H₂SO₄ solutions in the temperature range from 25 °C to 55 °C using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The results obtained from the both measurement techniques revealed good inhibitor efficiency in the studied concentration range. Nyquist plots showed depressed semicircles with their centre below real axis. Moreover, the impedance spectra in the case of both non inhibited solutions and inhibited ones by means of lower inhibitor concentrations exhibited Warburg impedance. The adsorption behaviour of ICA followed Langmuir’s isotherm.     

Corrosion behavior of alumina ceramics in aqueous HCl and H2SO4 solutions

The corrosion behavior of cold isostatically pressed (CIP) high purity alumina ceramics in aqueous HCl and H₂SO₄ solutions with various concentrations has been studied simultaneously at room temperature (25 °C). Corrosion tests were also performed with 0.65 mol/l HCl and 0.37 mol/l H₂SO₄ solutions at 40, 55 and 70 °C for 48 h. Chemical stability was monitored by determining the amount of Al³⁺, Mg²⁺, Ca²⁺, Na⁺ Si⁴⁺ and Fe³⁺ ions eluted in different concentrations of HCl and H₂SO₄ solutions by means of atomic absorption spectrometry (AAS). By increasing the concentration from 0.37 to 6.5 mol/l, it was notified that the corrosion susceptibility in HCl and H₂SO₄ solutions for the CIP alumina specimens at room temperature decreases.     

Synergistic inhibition behaviour of methylbenzyl quaternary imidazoline derivative and iodide ions on mild steel in H2SO4 solutions

The inhibition behaviour of 2-undecyl-1-ethylamino-1-methylbenzyl quaternary imidazoline (2UMQI) and KI on mild steel in 1.0 M H₂SO₄ solutions was investigated at 25 °C using electrochemical methods. The results indicated that 2UMQI inhibited the corrosion of mild steel and the extent of inhibition increased with 2UMQI concentrations. The inhibition action in the presence of 2UMQI is due to physical adsorption of 2UMQI. A mixed-inhibition mechanism is proposed for the inhibitive effects of 2UMQI. Inhibition efficiency of 2UMQI was enhanced by the addition of iodide ions. In the presence of KI, the potentials of unpolarization, E_u was observed and increased with KI concentration.     

Application of polyaniline to galvanic anodic protection on stainless steel in H2SO4 solutions

A stand-alone polyaniline (PANI) film electrode was made and then applied to protect 1Cr13 stainless steel (a type of stainless steel typically used in China, 0–15% C, 13% Cr) from corrosion in highly acidic solution, up to 5 M H₂SO₄. The stand-alone PANI electrode and 1Cr13 were coupled to study their galvanic interactions. PANI is a cathode while 1Cr13 is an anodic. The results indicate that PANI with a certain area can quickly passivate the stainless steel and effectively maintain the steady passive state for a long period of time. This specific method of PANI preventing 1Cr13 from corrosion is called galvanic anodic protection (GAP). Moreover, the efficiency, mechanism, and security of GAP were discussed. The results demonstrate that the stand-alone PANI electrode may have a potential application to galvanic anodic protection on stainless steel in highly corrosive H₂SO₄ solutions.     

A correlation between phosphorous impurity in stainless steel and a second anodic current maximum in H2SO4

Phosphorous as a minor element (0.03%) in AISI 304 austenitic stainless steel greatly affects the polarization and corrosion behavior in sulfuric acid solution. The presence of P in stainless steel created a second current maximum in the anodic polarization curve and the current increased with increasing aging in the solution. An adhesive corrosion surface layer, rich with phosphate, formed on the surface of a P-containing steel during active dissolution. The layer lowered the cathodic Tafel slope at low current densities, and is likely, due to a change in hydrogen evolution mechanism. Phosphorous increases the H-adsorbed (and/or absorbed) atoms on the surface, leading to the appearance of a second anodic current peak that is interpreted as re-oxidation of hydrogen atoms. Also, P shifted the corrosion potential to the noble side, decreased effectively the active anodic dissolution, and lowered the corrosion rate.