Holographic interferometry as electrochemical emission spectroscopy of a carbon steel in 5–20 ppm TROS C-70 inhibited seawater

In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the number of the fringe evolutions during the corrosion test of a carbon steel in blank seawater and seawater with different concentrations of a corrosion inhibitor. In other words, the anodic dissolution behaviors (corrosion) of the carbon steel were determined simultaneously by holographic interferometry, as an electromagnetic method, and by the electrochemical impedance (EI) spectroscopy, as an electronic method. So, the abrupt rate change of the number of the fringe evolutions during corrosion tests, EI spectroscopy, of the carbon steel is called electrochemical emission spectroscopy. The corrosion process of the steel samples was carried out in blank seawater and seawater with different concentrations, 5–20 ppm, of TROS C-70 corrosion inhibitor using the EI spectroscopy method, at room temperature. The electrochemical-emission spectra of the carbon steel in different solutions represent a detailed picture of the rate change of the anodic dissolution of the steel throughout the corrosion processes. Furthermore, the optical interferometry data of the carbon steel were compared to the data, which was obtained from the EI. spectroscopy. Consequently, holographic interferometry is found very useful for monitoring the anodic dissolution behaviors of metals, in which the number of the fringe evolutions of the steel samples can be determined in situ.     

Optical corrosion meter

In a previous study, a mathematical model relating surface and bulk behaviours of metals in aqueous solution has been developed. The model was established based on principles of holographic interferometry for measuring microsurface dissolution, i.e. mass loss, and on those of electrochemistry for measuring the bulk electronic current, i.e. corrosion current. In the present work, an optical corrosion meter was built based on the above model. The corrosion meter consists of an electrochemical cell in which the sample is immersed in aqueous solution. Furthermore, the corrosion meter has a holographic camera with a thermoplastic film for in situ processing of holograms in order to obtain real-time holographic interferoms of the sample in the electrochemical cell. Results of the present work indicate that optical holography is a very useful technique for measuring the corrosion current density of different alloys in aqueous solutions. As a result, the corrosion current density of aluminium, stainless steel, and low-carbon steel in 1 M KCl, 1 M NaCl, and 1 M NaOH solutions were obtained. A comparison between the corrosion data of samples showed that the corrosion current density of the stainless steel in 1 M NaCl is nearly three-folds higher than that of the aluminium in 1 M KCl and the low-carbon steel in 1 M NaOH.     

Investigation of the inhibitive effect of triphenyltin 2-thiophene carboxylate on corrosion of steel in 2 M H3PO4 solutions

A new organic compound was synthesised and tested as corrosion inhibitor of steel in phosphoric acid medium using gravimetric, electrochemical polarisation and electrochemical impedance spectroscopy (EIS) measurements. Results obtained show that the inhibitor studied is a good cathodic inhibitor. EIS results show that the change in the impedance parameters (R_T and C_dl) with concentration of triphenyltin 2-thiophene carboxylate (TTC) is indicative of the adsorption of molecules leading to the formation of a protective layer on the surface of steel. The effect of the temperature on the steel corrosion in 2 M H₃PO₄ and with addition of various concentrations of TTC in the range of temperature 298-348 K was studied. The associated apparent activation corrosion energy has been determined.     

Measurement of the corrosion rate of aluminium in sodium hydroxide using holographic interferometry

The application of holographic interferometry to the measurement of the corrosion rate of aluminium in sodium hydroxide is investigated. Details of the fabrication of the corrosion cell and the experimental procedure are given. Thickness loss of aluminium was found for different dissolution times and compared with the conventional weight-loss method using a microbalance.     

Modified electrochemical emission spectroscopy (MEES) As technique of NDT for detection localized corrosion of copper alloys in seawater

An early stage of localized corrosion, i.e., pitting and crevice corrosion, of a pure copper and a brass in uncoated and coated conditions in seawater was investigated in situ by a new non-destructive testing (NDT) method. The new method of localized corrosion detection is based on the optical corrosion-meter for measuring the corrosion current density (J) and on a modified electrochemical noise technique for determining the corrosion admittance (A_c) at the open-circuit potential of the alloys in solutions. The observations of localized corrosion were basically interferometric perturbations detected by the optical corrosion-meter only on the uncoated copper and the coated brass at the beginning of the tests. The interferometic perturbations interpreted as a localized corrosion in the form of an early pitting and crevice corrosion, of a depth ranging from 0.3 μm to several micrometers, of the uncoated copper and the coated brass, respectively. Also, the early stage of localized corrosion of the same alloys in the same conditions was determined in situ by a modified electrochemical noise (EN) technique, called the modified electrochemical emission spectroscopy (MEES) technique, simultaneously during the optical interferometry measurements. Determinations of localized corrosion by the MEES technique were electrochemical noise spectra detected on corrosion admittance (A_c)-time plots of the alloys in solutions. The corrosion admittance parameter, A_c=(dJ/dV), which defined the MEES technique, is capable of indicating localized corrosion and uniform corrosion activities. In this investigation, the parameter A_c was modified in which the change of the corrosion current density (dJ) was measured by the optical corrosion-meter rather than by the zero resistance ammeter, which is usually used for measuring the dJ in electrochemical noise technique. Consequently, results of the present work indicate that optical corrosion-meter as an electromagnetic method of measuring the corrosion current density, and MEES technique, as an electronic method for determining the A_c, are very useful techniques as non-destructive methods for the detection of localized corrosion at the initiation stage of the phenomenon.     

Localized dissolution electrochemistry at surface irregularities of pipeline steel

The localized electrochemical dissolution behavior at surface irregularities, including scratch, mechanically induced hole and corrosion pit, on pipeline steel was investigated in both near-neutral pH and high pH solutions by scanning vibrating micro-electrode and localized electrochemical impedance spectroscopy measurements. In near-neutral pH solution, the localized dissolution behavior at surface irregularities is dependent of their geometrical depth, which is critical to development of a local electrochemical condition to support the further localized dissolution. Therefore, surface irregularities exceeding a certain depth provide potential sites to initiate stress corrosion cracks in near-neutral pH solution. The strong passivating capability of high pH solution would result in the formation of oxide film over the whole electrode surface to “equalize” the electrochemical activity at irregularities to the intact area. Therefore, the irregularities would not result in localized dissolution electrochemistry. Consequently, localized corrosion and crack initiation are not anticipated to initiate from the geometrical irregularities in high pH solution. However, corrosion pits generating due to passive film breakdown could support the high local dissolution kinetics in high pH solution, providing potential sites for crack initiation. The effects of hydrogen-charging on anodic dissolution at regularities depend on the defect geometry and the solution pH.     

An electroactive co-polymer as corrosion inhibitor for steel in sulphuric acid medium

The corrosion behavior of mild steel in sulphuric acid solution containing various concentrations of a co-polymer formed between maleic anhydride and N-vinyl-2-pyrrolidone (VPMA) was investigated using weight-loss, polarization and electrochemical impedance techniques. The polymer acts as an effective corrosion inhibitor for steel in sulphuric acid medium. The inhibition process is attributed to the formation of an adsorbed film of co-polymer on the metal surface which protects the metal against corrosion. Scanning electron microscopy (SEM) studies of the metal surfaces confirmed the existence of an adsorbed film. The adsorption followed the Langmuir isotherm. The protection efficiency increased with increase in inhibitor concentration and decreased with increase in temperature and acid concentration. The thermodynamic functions of the adsorption and dissolution processes were evaluated.     

Electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy study of the corrosion behaviour of galvanized steel and electroplating steel

The efficiency of a formula containing 2-{(2-hydroxyethyl)[(4-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amino}ethanol (tolyltriazole) and decanoic acid as corrosion inhibitor for galvanized steel and electroplating steel in aqueous solution have been determined by electrochemical impedance spectroscopy (EIS) techniques. The experimental data obtained from this method show a frequency distribution and therefore a modelling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. The corrosion behaviour in the presence of different concentration of decanoic acid (DA) in the formula was also investigated by EIS. Results obtained reveal that, the formula is a good inhibitor for galvanized steel and electroplating steel in aqueous solution, the better performance was obtained in the case of galvanized steel. The ability of the inhibitor to be adsorbed on the surface was dependent on the nature of metal. X-ray photoelectron spectroscopy surface analysis with inhibitor shows that it's chemisorbed at the galvanized and electroplating steel/aqueous solution interface.     

Characteristics of CO2 corrosion scale formed on N80 steel in stratum water with saturated CO2

The component and structure of CO₂ corrosion scale formed on N80 tubing steel were studied by using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM); the electrochemical property of N80 steel covered by corrosion scale was investigated by electrochemical impedance spectroscopy (EIS). The results shows a double-layer structure of the corrosion scale, in which the principal component of the outer layer is FeCO₃ with a limited amount of ∂-FeOOH; while for the inner scale, FeCO₃ is still the major component, but some Fe positions in FeCO₃ lattice are substituted by Ca, and form a composite compound of (Fe,Ca)CO₃ in the inner scale. EIS study shows that the anodic impedance spectrum has three time constants, i.e., the capacitance at high frequency, Warburg impedance at middle frequency and capacitance at low frequency.     

Synthesis, characterization, and corrosion protection properties of poly(N-(methacryloyloxymethyl) benzotriazole-co-methyl methacrylate) on mild steel

The copolymers from different feed ratios of N-(methacryloyloxymethyl) benzotriazole (MMBT) and methyl methacrylate (MMA) has been synthesised using free radical solution polymerization technique and characterized using FT-IR and ¹³C NMR spectroscopy. The thermal stability of the polymers was studied using theremogravimetrtic analysis (TGA). The corrosion behaviors of mild steel specimens dip coated with different composition of copolymers have been evaluated by potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) method. These electrochemical properties were observed in 0.1 M HCl medium. The polarization and impedance measurements showed different corrosion protection efficiency with change in composition of the copolymers. It was found that the corrosion protection properties are owing to the barrier effect of the polymer layer covered on the mild steel surfaces. However, it was observed that the copolymer obtained from 1:1 mole ratio of MMBT and MMA exhibited better protection efficiency than other combinations.     

Preparation of the Ni-P composite coating co-deposited by nano TiC particles and evaluation of it's corrosion property

In current research, low carbon steel plates were coated by Ni-P electroless method. The effect of adding different concentrations (ranging from 0.01 g/l to 0.5 g/l) of TiC nano-sized particles to the plating bath on deposition rate, surface morphology and corrosion behavior of Ni-P-TiC composite coatings were investigated. The surface morphology and the relevant structure were evaluated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Corrosion behavior of the coated steel was evaluated by electrochemical impedance spectroscopy (EIS) and polarization techniques. The results showed that addition of TiC nano-particles to Ni-P electroless bath not only changes the surface morphology of Ni-P coating, but also improves corrosion resistance of the steel in comparison with TiC free Ni-P electroless coating. In addition, the deposition rate of coating was also affected by incorporation of TiC particles. It was also found that improvement in corrosion resistance largely depends on the phosphorous and TiC concentrations on the coatings.     

Inhibitive action of indole-5-carboxylic acid towards corrosion of mild steel in deaerated 0.5 M sulfuric acid solutions

Inhibition of mild steel corrosion in deaerated 0.5 M sulfuric acid solutions containing various concentrations of indole-5-carboxylic acid is studied in the temperature range from 25 to 55 °C using weight-loss, potentiodynamic and spectrophotometric tests. The adsorptive behaviour of inhibitor is also investigated using electrochemical impedance spectroscopy measurements. The indole-5-carboxylic acid is found to shift the corrosion potentials towards more noble values. This shift indicates that the addition of inhibitor mainly affects the anodic process, raising the anodic overpotential more than that of the cathodic, i.e. the indole-5-carboxylic acid behaves as mixed-type inhibitor. Because the cathodic Tafel slopes for hydrogen reduction (b_c) are affected, the inhibitor probably affects the hydrogen reduction mechanism. The activation energy values (E_a) indicate that the indole-5-carboxylic acid increases the activation energy of the corrosion reaction. The adsorption behaviour of indole-5-carboxylic acid follows Langmuir's isotherm. Both the low values of and its decrease with temperature suggest physical adsorption. Double layer capacitance-potential curves indicate considerable adsorption of the inhibitor in the potential range (−400 to −800 mV/_SCE).     

The adsorption behavior and corrosion inhibition mechanism of anionic inhibitor on galvanic electrode in 1% NaCl solution

The adsorption behavior of dodecanoic acid and its sodium salt (DDAS) as an anionic inhibitor on the galvanic electrode has been investigated by using electrochemical methods, Fourier transform infrared spectroscopy (FT-IR), and atomic force microscopy (AFM). The galvanic electrode was prepared by coupling N80 carbon steel (CS) and S31803 stainless steel (SS), and all experiments were performed in NaCl solution at pH 4 in the presence or absence of DDAS. Electrochemical experiments reveal SS and CS carry positive and negative excess charges in NaCl solution at pH 4, and DDAS is mainly anodic type inhibitor for the galvanic corrosion. FT-IR and AFM were used to analyze the protective layer formed on the electrodes, a stronger adsorbability of the inhibitor on the anode (CS) of GE was measured. Results indicate the protective layer formed on the single CS electrode is less compact than which on the coupled CS. The adsorption regulation of anionic inhibitor on the galvanic electrode is summarized based on the results obtained from electrochemical methods, FT-IR and AFM.     

Electrochemical, theoretical and XPS studies of 2-mercapto-1-methylimidazole adsorption on carbon steel in 1 M HClO4

The inhibition of the corrosion of carbon steel in 1 M HClO₄ by 2-mercapto-1-methylimidazole (MMI) has been investigated in relation to the concentration of the inhibitor as well as the temperature using weight loss and electrochemical measurements. 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. Polarization curves reveal that MMI is a mixed type inhibitor. The inhibition efficiency of MMI is temperature independent but increases with the inhibitor concentration. Changes in impedance parameters (charge transfer resistance, R_t, and double-layer capacitance, C_dl) were indicative of adsorption of MMI on the metal surface, leading to the formation of a protective film. Adsorption of MMI on the carbon steel surface is found to obey the Langmuir adsorption isotherm. Some thermodynamic functions of dissolution and adsorption processes were also determined. The X-ray photoelectron spectroscopy (XPS) of the carbon steel indicated that MMI is chemically adsorbed on the steel surface. Moreover, the electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels and molecular orbital densities were calculated.     

Enhanced corrosion resistance of mild steel in molar hydrochloric acid solution by 1,4-bis(2-pyridyl)-5H-pyridazino[4,5-b]indole: Electrochemical, theoretical and XPS studies

The inhibition effect of the new pyridazine derivative, namely 1,4-bis(2-pyridyl)-5H-pyridazino[4,5-b]indole (PPI) against mild steel corrosion in 1 M HCl solutions was evaluated using weigh loss and electrochemical techniques (potentiodynamic polarisation curves and impedance spectroscopy). The experimental results suggest that PPI is a good corrosion inhibitor and the inhibition efficiency increased with the increase of PPI concentration, while the adsorption followed the Langmuir isotherm. X-ray photoelectron spectroscopy (XPS) and theoretical calculation of electronic density were carried out to establish the mechanism of corrosion inhibition of mild steel with PPI in 1 M HCl medium. The inhibition action of this compound was, assumed to occur via adsorption on the steel surface through the active centres contained of the molecule. The corrosion inhibition is due to the formation of a chemisorbed film on the steel surface.     

Interferometric Sensor for Electrochemical Studies of Metallic Alloys in Aqueuos Solution

In a previous study a mathematical model relating surface and bulk behaviors of metals in aqueous solution was developed. The model was established based on principles of holographic interferometry for measuring microsurface dissolution, i.e., mass loss, and on those of electrochemistry for measuring the bulk electronic current, i.e., corrosion current. In the present work, an interferometric sensor was built based on the above model, and the corrosion current density of coated copper and brass in seawater were obtained using this sensor. The interferometric sensor was also utilized for the first time to measure the initial stage of the anodization process (oxidation) of aluminium samples in aqueous solution. This was carried out chemically in different acid concentrations (3.125–25% H₂SO₄) at room temperature. The sensor was further used for observation of catalytic activities, i.e., pitting corrosion, which occurred subsequent to the anodization of the aluminium samples in aqueous solutions, after an oxide film had been formed.     

Development of electroless Ni-Zn-P/nano-TiO2 composite coatings and their properties

Ni-Zn-P-TiO₂ composite coatings were successfully obtained on low carbon steel by electroless plating technique. Deposits were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive analysis (EDS) studies. The hardness and microstructure of as plated and heat treated Ni-Zn-P and Ni-Zn-P-TiO₂ composite coatings were analyzed. The change in microstructure and higher hardness was noticed for heat treated composite. The corrosion resistance behavior of as plated and heat treated Ni-Zn-P and Ni-Zn-P-TiO₂ coatings was investigated by anodic polarization, Tafel plots and electrochemical impedance spectroscopic (EIS) studies in 3.5 wt% NaCl solution. The composite coating exhibited enhanced corrosion resistance property over Ni-Zn-P coating.     

Inhibition of steel corrosion in 2 M H3PO4 by artemisia oil

Artemisia oil (Ar) is extracted from artemisia herba alba collected in Ain es-sefra-Algeria, and tested as corrosion inhibitor of steel in 2 M H₃PO₄ using weight loss measurements, electrochemical polarisation and EIS methods. The naturally oil reduces the corrosion rate. The inhibition efficiency was found to increase with oil content to attain 79% at 6 g/l. Ar acts as a cathodic inhibitor. The effect of temperature on the corrosion behaviour of steel indicates that inhibition efficiency of the natural substance decreases with the rise of temperature. The adsorption isotherm of natural product on the steel has been determined.     

1,3-Bis(3-hyroxymethyl-5-methyl-1-pyrazole) propane as corrosion inhibitor for steel in 0.5 M H2SO4 solution

The effect of addition of 1,3-bis(3-hyroxymethyl-5-methyl-1-pyrazole) propane (M = 264 g). HMPP on steel corrosion in 0.5 M sulphuric acid is studied by weight-loss, electrochemical polarisation and electrochemical impedance spectroscopy (EIS) measurements at various temperatures. The results obtained showed that HMPP acts as a good corrosion inhibitor. The inhibition efficiency increases with the bipyrazole compound to attain 88%. It acts as a mixed-type inhibitor. Trends in the increase of charge-transfer resistance and decrease of capacitance values also show the adsorption of the molecule on the metal surface. The bipyrazole adsorbs on the steel surface according to the Langmuir isotherm adsorption model. Effect of temperature indicates that inhibition efficiency decreases with temperature between 25 and 85 °C.