Corrosion and corrosion control of mild steel in concentrated H2SO4 solutions by a newly synthesized glycine derivative

A newly synthesized glycine derivative (GlyD1), 2-(4-(dimethylamino)benzylamino)acetic acid hydrochloride, was used to control mild steel corrosion in 4.0 M H₂SO₄ solutions at different temperatures (278–338 K). Tafel extrapolation, linear polarization resistance (LPR) and impedance methods were used to test corrosion inhibitor efficiency. An independent method of chemical analysis, namely ICP-AES (inductively coupled plasma atomic emission spectrometry) was also used to test validity of corrosion rate measured by Tafel extrapolation method. Results obtained were compared with an available glycine derivative (GlyD2) and glycine (Gly). Tafel polarization measurements revealed that the three tested inhibitors function as mixed-type compounds. The inhibition efficiency increased with increase in inhibitor concentration and decreased with temperature, suggesting the occurrence of physical adsorption. The adsorptive behaviour of the three inhibitors followed Temkin-type isotherm and the standard free energy changes of adsorption () were evaluated for the three tested inhibitors as a function of temperature. The inhibition performance of GlyD1 was much better than those of GlyD2 and Gly itself. Results obtained from the different corrosion evaluation techniques were in good agreement.     

Testing validity of the Tafel extrapolation method for monitoring corrosion of cold rolled steel in HCl solutions - Experimental and theoretical studies

The protection influence of glycine (Gly) and a one of its derivatives, namely 2-(bis(2-aminoethyl)amino) acetic acid, designated here as GlyD; where GlyD stands for “glycine derivative”, against cold rolled steel (CRS) corrosion was studied in aerated stagnant 1.0 M HCl solutions at 25 °C. Measurements were conducted under various experimental conditions using Tafel polarization, linear polarization and impedance techniques. These studies have shown that Gly and GlyD are very good “green”, mixed-type inhibitors. GlyD is more effective than Gly itself in inhibiting the acid corrosion of CRS. Electrochemical frequency modulation (EFM) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) method of analysis are also presented here for monitoring corrosion. Corrosion rates obtained from both EFM and ICP-AES methods are comparable with those recorded using Tafel extrapolation method, confirming validation of corrosion rates measured by the latter. Adsorption via H-bond is discussed here, based on the presence of oxide film on the electrode surface as well as the number of NH linkages in the inhibitor molecule. Quantum chemical method was also employed to explore the relationship between the inhibitor molecular properties and its protection efficiency. The density function theory (DFT) is used to study the structural properties of Gly and GlyD in aqueous phase in an attempt to understand their inhibition mechanism. The protection efficiencies of these compounds showed a certain relationship to highest occupied molecular orbital (HOMO) energy, Mulliken atomic charges and Fukui indices.     

Pitting corrosion of artificially aged T6 AA2024/SiCp composites in 3.5 wt.% NaCl aqueous solution

The pitting corrosion behavior of the underaged (UA), peakaged (PA) and overaged (OA) T6 AA2024/0, 8, 14, 19, 24 vol.% 40 μm SiC_p(particles) composites was studied. The processing route used for the materials was the compocasting technique. Corrosion potentials (E_cor), pitting potentials (E_pit) as well as protection potentials (E_prot) were extracted from Double Cycle Polarization (DCP) curves contacted in aerated 3.5 wt.% NaCl aqueous solution. In addition 40 days immersion tests carried out and weight loss curves as well as total pit depth measurements were acquired. Pitting initiation and propagation as the main corrosion mechanism was driven by the aging kinetics which is ruled by the reduction in the retained vacancy concentration and at the same time by the increase in dislocation density as SiC_p volume fraction increases. Thus, alteration in pitting behavior among composites of different SiC_p content took place, although their ageing status was exactly the same.     

Chronoamperometric studies of pitting corrosion of Al and (Al-Si) alloys by halide ions in neutral sulphate solutions

The pitting corrosion of Al, (Al + 6%Si), and (Al + 18%Si) alloys in neutral 0.50 M Na₂SO₄ solution in the absence and presence of NaCl, NaBr and NaI under the influence of various experimental variables has been studied by using potentiodynamic and chronoamperometric techniques. The results showed that the pitting corrosion resistance of the three Al samples decreases in the order: (Al + 18%Si) > (Al + 6%Si) > Al. The current/time measurements showed that the overall process can be described by three stages. The first stage corresponds to the nucleation and growth of a passive oxide layer. The second and the third stages involving pit nucleation and growth, respectively. Nucleation of pit takes place after an incubation time (t_i). The rate of pit nucleation (t_i⁻¹) increases with increasing halide concentration, temperature, and applied potential. The pit growth current density (j_pit) increases linearly with t^1/2, indicating that the pit growth can be described in terms of an instantaneous three dimensional growth under diffusion control. The effect of Cr₂O₇²⁻, CrO₄²⁻, WO₄²⁻, MoO₄²⁻, NO₂⁻ and NO₃⁻ as inorganic inhibitors on the pitting corrosion inhibition of pure Al and its alloys in (0.5 M Na₂SO₄ + 0.2 M NaCl) solution has also been studied. The presence of these anions (except NO₃⁻) results in an increase in the incubation time and a decrease in the pit growth current density of the three samples to an extent depending on the nature and the concentration of the inorganic inhibitors and the composition of the Al samples. The inhibition efficiency of these inhibitors decreases in the order: Cr₂O₇²⁻ > CrO₄²⁻ > WO₄²⁻ > MoO₄²⁻ > NO₂⁻.     

Pitting and pitting control of Al in gluconic acid solutions - Polarization, chronoamperometry and morphological studies

The anodic behaviour of Al in gluconic acid (HG) solutions was studied. Al was found to pit in such solutions. Surface and cross-sectional views of the SEM images recorded beyond the breakdown potential (E_b) revealed the occurrence of intense pitting attack with the formation of large hemispherical pits. The effect of adding some environmentally acceptable inorganic inhibitors (tungstates, molybdates or silicates) on the pitting corrosion behaviour of Al in HG solutions was also studied. Measurements were carried out under the influence of various experimental variables based on polarization and chronoamperometric techniques. These measurements were complemented by ex situ scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) examinations of the electrode surface. The presence of these compounds in HG solutions decreased the passive current density (j_pass) and increased E_b. In HG solutions, chronoamperometric measurements showed that the anodic current density first decreased, due to growth of a passive oxide film, then increased with time after a pit incubation time, t_i and finally attained a steady-state value. Value of t_i was shortened and simultaneously the steady-state current was elevated, corresponding to an increase in the rate of pit initiation and growth, with increasing applied anodic potential and HG concentration. The rate of pit nucleation () was found to decrease to an extent depending on the type and concentration of the introduced inhibitor. The inhibitory effect of these compounds decreased in the order:  >  > .     

Electrochemical pitting corrosion behaviour of α-brass in LiBr containing solutions

The potentiodynamic anodic polarization curve of α-brass (70% Cu-30% Zn) in 1 M LiBr solution showed an initial active region of the alloy dissolution followed by two well defined anodic current peaks then a narrow passivation region before the pitting potential (E_pit) is reached. The initial active anodic region exhibited Tafel slope with 90 mV dec⁻¹ attributed to the formation of CuBr₂⁻ complexes. The anodic current peaks were attributed to the formation of CuBr and Cu²⁺ ions, respectively. The change of pH values of LiBr solution did not affect the anodic polarization curves of α-brass. Increasing the solution temperature from 30 to 90 °C changed the corrosion type from pitting to general one. The addition of 10⁻² M benzotriazole (BTAH) to 1 M LiBr solution is completely inhibited the pitting corrosion at 30 °C while it did not inhibit the pitting at 90 °C. The inhibition effect was attributed to the adsorption of BTAH molecules on the alloy surface, which obeys Langmuir isotherm. The presence or absence of pitting corrosion was confirmed by using SEM.     

Microstructure and corrosion behaviour of pulsed plasma-nitrided AISI H13 tool steel

The effect of pulsed plasma nitriding temperature and time on the pitting corrosion behaviour of AISI H13 tool steel in 0.9% NaCl solutions was investigated by cyclic polarization. The pitting potential (E_pit) was found to be dependent on the composition, microstructure and morphology of the surface layers, whose properties were determined by X-ray diffraction and scanning electron microscopy techniques. The best corrosion protection was observed for samples nitrided at 480 °C and 520 °C. Under such experimental conditions the E_pit-values shifted up to 1.25 V in the positive direction.     

Pitting corrosion behaviour of austenitic stainless steels with Cu and Sn additions

The influence of Cu and Sn on the pitting corrosion resistance of AISI 304 and 316 stainless steels in chloride-containing media has been investigated. The corrosion behaviour was evaluated by cyclic polarization, potentiostatic CPT measurements and electrochemical impedance spectroscopy in 3.5 wt% NaCl. The corrosion resistance was also studied in FeCl₃ under Standard ASTM G-48. According to the results, Cu addition favours pit nucleation but inhibits its growth, whereas Sn exerts the opposite effect, favouring pit growth and inhibiting its nucleation. Studies by SEM, X-ray mapping and EDS analysis showed Cu-, Cl- and O-rich corrosion products that reduce the extent of corrosion damage.     

Influence of reinforcement proportion and matrix composition on pitting corrosion behaviour of cast aluminium matrix composites (A3xx.x/SiCp)

The influence of silicon carbide (SiCp) proportion and matrix composition on four aluminium metal matrix composites (A360/SiC/10p, A360/SiC/20p, A380/SiC/10p, A380/SiC/20p) immersed in 1-3.5 wt% NaCl at 22 °C was investigated by potentiodynamic polarization. The kinetics of the corrosion process was studied on the basis of gravimetric measurements. The nature of corrosion products was analysed by scanning electron microscopy (SEM) and low angle X-ray diffraction (XRD). The corrosion damage in Al/SiCp composites was caused by pitting attack and by nucleation and growth of Al₂O₃ · 3H₂O on the material surface. The main attack nucleation sites were the interface region between the matrix and the reinforcement particles. The corrosion process was influenced more by the concentration of alloy elements in the matrix than by the proportion of SiCp reinforcement and saline concentration.     

Study of the electrochemical behaviour of nanocrystalline zinc by statistical methods

Pulse electrodeposition was used to synthesize nanocrystalline (NC) zinc coatings from citric acid bath. The electrochemical behaviour of the NC zinc coatings was investigated by using potentiostatic and potentiodynamic polarization methods in 0.5 mol/L NaCl (pH = 12) solution and compared with that of cast zinc. Pitting corrosion behaviour was characterized by pitting potential, induction time and stable pit growth rate which were analyzed according to statistical method. The results showed that nanocrystallization increased the sensitivity of E_pit refer to potential sweep velocity, changed the type of the pit generation from B1 (parallel) to B2 (series), accelerated the pitting initiation process and inhibited the stable pit growth process of NC zinc.     

Effects of pH and chloride concentration on pitting corrosion of AA6061 aluminum alloy

Effects of pH solution and chloride (Cl⁻) ion concentration on the corrosion behaviour of alloy AA6061 immersed in aqueous solutions of NaCl have been investigated using measurements of weight loss, potentiodynamic polarisation, linear polarisation, cyclic polarisation experiment combined with open circuit potential transient technique and optical or scanning electron microscopy.The corrosion behaviour of the AA6061 aluminum alloy was found to be dependant on the pH and chloride concentration [NaCl] of solution. In acidic or slightly neutral solutions, general and pitting corrosion occurred simultaneously. In contrast, exposure to alkaline solutions results in general corrosion. Experience revealed that the alloy AA6061 was susceptible to pitting corrosion in all chloride solution of concentration ranging between 0.003 wt% and 5.5 wt% NaCl and an increase in the chloride concentration slightly shifted both the pitting E_pit and corrosion E_cor potentials to more active values. In function of the conditions of treatment, the sheets of the alloy AA6061 undergo two types of localised corrosion process, leading to the formation of hemispherical and crystallographic pits.Polarisation resistance measurements in acidic (pH = 2) and alkaline chloride solutions (pH = 12) which are in good agreement with those of weight loss, show that the corrosion kinetic is minimised in slightly neutral solutions (pH = 6).     

The metastable pitting behaviors of mild steel in bicarbonate and nitrite solutions containing Cl

The metastable pitting behaviors of mild steel in NaHCO₃ + NaCl and NaNO₂ + NaCl solutions were studied with electrochemical methods. In NaHCO₃ + NaCl solution the potential range between metastable pitting potential E_m and pitting potential E_b is relatively large, and most of the current fluctuations are individual. While in NaNO₂ + NaCl solution the E_m and E_b values are much higher and the potential range between them is very narrow, leading to overlapped current peaks. The changes of E_m and E_b with chloride concentration follow similar tendency. In both testing solutions, the repassivated metastable pitting sites are prone to become preferential sites for following metastable pits to nucleate, leading to accumulated corrosion damages on the surface. Mild steel shows stronger passivity in NaNO₂ + NaCl solution than in NaHCO₃ + NaCl solution, which explains the higher pitting resistance of the steel in the former. In addition, the competitive adsorption of anions also plays an important role in the increase of E_m and E_b, especially in inhibiting nucleation of metastable pits.     

Investigating accuracy of the Tafel extrapolation method in HCl solutions

This paper discusses the validity and accuracy of the Tafel extrapolation method for determining corrosion rates of carbon steel in 1, 2 and 3 M HCl solutions open to air. Corrosion rates obtained from polarization experiments were compared with that of weight loss method. For analysing data obtained from polarization experiments electrochemical impedance spectroscopy (EIS) measurements were performed before polarization experiments. The results showed that formation of a corrosion product film and increasing the polarization resistance (R_p) of this film with time cause the corrosion rates obtained from Tafel extrapolation tend to be higher than corrosion rates obtained from weight loss test.     

Semiconducting and passive film properties of nitrogen-containing type 316LN stainless steels

The semiconducting property of passive films of nitrogen-containing type 316LN stainless steels in different electrolytic media (0.5 M NaCl, borate buffer and borate buffer + 0.5 M NaCl) was investigated by electrochemical impedance spectroscopy (EIS). The nitrogen effect on the chemical composition of the passive films was investigated using X-ray photoelectron spectroscopy, (XPS). Based on capacitance results, the semiconducting parameters obtained from the Mott-Schottky plots indicated a decrease in the donor and acceptor density (N_D and N_A) with increase in nitrogen content, and variation in the flat band potential (E_FB), depending on the electrolytic media. Thus indicating that the oxide layers of the passive film are modified by nitrogen addition. The presence of nitrogen and in the passive film was confirmed by the XPS analysis of the passive film. Cyclic polarization for pitting and repassivation corrosion studies indicated a decrease in hysteresis loop with increase in nitrogen content in 0.5 M NaCl solution. In the highest nitrogen-containing alloy (0.556 wt.% N), the hysteresis loop was small and negligible indicating that the pit initiation is minimum in this alloy. Based on the results obtained, an attempt was made to correlate the semiconducting nature of the passive films with pitting corrosion resistance.     

Pitting corrosion mechanism of Type 304 stainless steel under a droplet of chloride solutions

Pitting corrosion of Type 304 stainless steel under drops of MgCl₂ solution has been investigated to clarify the rusting mechanism in marine atmospheres. A pitting corrosion test was performed under the droplets with various combinations of the diameter and thickness (height) by exposure to a constant relative humidity. Probability of occurrence of pitting corrosion decreased with decreasing the diameter and thickness. Pitting corrosion progressed only when the [Cl⁻] exceeded 6 M (RH < 65%). In almost cases, there was a small hole (∼10 μm diameter) in the center of a single pit, which may be the trace of an inclusion particle like MnS dissolved out. The pitting corrosion mechanism of Type 304 under droplets containing chloride ions has been proposed.     

Electrochemical corrosion behaviour of microcrystalline aluminium in acidic solutions

The electrochemical corrosion behaviour of microcrystalline pure aluminium coating, fabricated by a magnetron sputtering technique, has been investigated in both 0.5 mol/l NaCl and 0.5 mol/l Na₂SO₄ acidic (pH = 2) aqueous solutions. The corrosion resistance of the microcrystalline Al coating has deteriorated more compared with that of the cast pure Al in Na₂SO₄ acidic solution. However, its oxide film has a higher pitting resistance in the NaCl acidic solution. Chloride ions play a big role in the formation of the oxide film on the microcrystalline Al coating. The higher pitting resistance was attributed to the more acidic isoelectric point which the oxide film achieved.     

Environmental factors affecting the corrosion behavior of reinforcing steel III. Measurement of pitting corrosion currents of steel in Ca(OH)2 solutions under natural corrosion conditions

Using a simple electrolytic cell, the pitting corrosion current of reinforcing steel is measured in Ca(OH)₂ solutions in presence of chloride and sulfate as aggressive ions. Pitting corrosion current starts to flow after an induction period which depends on the concentration of both the aggressive and the passivating anions. The pitting corrosion current densities reach steady-state values which depend also on the type and concentration of the corrosive and passivating anions. The corrosive action of the aggressive species decreased in the order: SO₄²⁻ > Cl⁻. Corrosion of the steel is found to be governed by a single electron transfer reaction. Raising the temperature decreases the induction period associated with pit initiation and increases the corrosion current associated with pit propagation. From Arrhenius plots, the activation energies for both pit initiation and pit propagation in presence of chloride and sulfate ions are calculated.     

Electrochemical passive properties of AlxCoCrFeNi (x = 0, 0.25, 0.50, 1.00) alloys in sulfuric acids

This study investigates the electrochemical passive properties of Al_xCoCrFeNi alloys in H₂SO₄ by potentiodynamic polarization, EIS, and weight loss tests from 20 to 65 °C. Experimental results indicate that Al harms the corrosion resistance in H₂SO₄ at temperatures exceeding 27 °C owing to the porous and inferior nature of the protection oxide film of Al in these alloys. Closely examining the Arrhenius plots of corrosion current density reveals that both pre-exponential factor A and activation energy E_a increase with Al content. However, A affects corrosion current density more significantly than E_a at higher temperatures and, conversely, at lower temperatures.     

Repassivation of the damage generated by cavitation on UNS N08031 in a LiBr solution by means of electrochemical techniques and Confocal Laser Scanning Microscopy

The objective of this work is to study the influence of cavitation on the corrosion behaviour of Alloy 31, a highly-alloyed austenitic stainless steel (UNS N08031), in a LiBr heavy brine solution (992 g/L) at 25 °C. The presence of cavitation shifted the OCP value towards the active direction by 708 mV_Ag/AgCl, increased anodic current densities and passivation current density, i_p, and reduced the pitting potential, E_p.Repassivation behaviour of Alloy 31 has been investigated by using potentiostatic tests at different potentials. The current density transient obtained after interrupting cavitation was used to obtain the repassivation index, n, provided by the slope of the log i(t) vs. log t representation. The value of n decreased as the applied potential was increased, reaching values near zero for potentials close to the pitting potential. The damage generated during the potentiostatic tests has been quantified by means of Confocal Laser Scanning Microscopy.     

Pitting corrosion behaviour of austenitic stainless steels - combining effects of Mn and Mo additions

Mn and Mo were introduced in AISI 304 and 316 stainless steel composition to modify their pitting corrosion resistance in chloride-containing media. Corrosion behaviour was investigated using gravimetric tests in 6 wt.% FeCl₃, as well as potentiodynamic and potentiostatic polarization measurements in 3.5 wt.% NaCl. Additionally, the mechanism of the corrosion attack developed on the material surface was analysed by scanning electron microscopy (SEM), X-ray mapping and energy dispersive X-ray (EDX) analysis. The beneficial effect of Mo additions was assigned to Mo⁶⁺ presence within the passive film, rendering it more stable against breakdown caused by attack of aggressive Cl⁻ ions, and to the formation of Mo insoluble compounds in the aggressive pit environment facilitating the pit repassivation. Conversely, Mn additions exerted an opposite effect, mainly due to the presence of MnS inclusions which acted as pitting initiators.