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.     

Electrochemical behaviour of aluminium/steel rivet joints

The galvanic corrosion behaviour of a rivet joint of two sheets of the aluminium alloys EN AW-6014-T4 and EN AW-6082-T5 joined by an electrogalvanized steel blind rivet was investigated. The potentiodynamic polarization curves in a 5 wt.% NaCl solution show a potential reversion of the anodic and cathodic regions of the rivet joint. The surface potential was investigated with a capillary electrode before and after corrosion. From the measurements by the capillary electrode and SEM-observations an improved resistance against galvanic corrosion is expected after the dissolution of the zinc layer of the blind rivet.     

Comparison of susceptibility to pitting corrosion of AA2024-T4, AA7075-T651 and AA7475-T761 aluminium alloys in neutral chloride solutions using electrochemical noise analysis

The susceptibility to pitting corrosion of AA2024-T4, AA7075-T651 and AA7475-T761 aluminium alloys was investigated in aqueous neutral chloride solution for the purpose of comparison using electrochemical noise measurement. The experimentally measured electrochemical noises were analysed based upon the combined stochastic theory and shot-noise theory using the Weibull distribution function. From the occurrence of two linear regions on one Weibull probability plot, it was suggested that there existed two stochastic processes of uniform corrosion and pitting corrosion; pitting corrosion was distinguished from uniform corrosion in terms of the frequency of events in the stochastic analysis. Accordingly, the present analysis method allowed us to investigate pitting corrosion independently. The susceptibility to pitting corrosion was appropriately evaluated by determining pit embryo formation rate in the stochastic analysis. The susceptibility was decreased in the following order: AA2024-T4 (the naturally aged condition), AA7475-T761 (the overaged condition) and AA7075-T651 (the near-peak-aged condition).     

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.     

Effect of α-Al/Al3Ni microstructure on the corrosion behaviour of Al-5.4 wt% Ni alloy fabricated by equal-channel angular pressing

The effect of microstructure on corrosion behaviour of an Al-5.4 wt% Ni alloy fabricated by equal-channel angular pressing (ECAP) was investigated by means of potentiodynamic polarization test. The Al-5.4 wt% Ni alloy samples were severely deformed by ECAP with two strain introduction methods of route A and route B_C and the ECAP process was repetitively carried out up to 6 passes (strain 6). The anodic polarization measurements indicated that pitting potential of the ECAPed Al-Ni alloy samples in chloride containing neutral buffer solution increased with ECAP passes. The pitting corrosion resistance of Al-Ni alloy after ECAP by route B_C was better than that by route A. It is attributable to that the size of α-Al crystal region was reduced with ECAP passes and route B_C was able to obtain more homogeneous α-Al/Al₃Ni structure than route A. On the other hand, pitting corrosion resistance of pure Al samples showed an obvious declining with increasing ECAP passes. It was indicated that more homogeneous and finer α-Al/Al₃Ni structure obtained by ECAP played a vital role on improving the corrosion resistance of Al-5.4 wt% Ni alloy.     

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.     

Pitting corrosion of intermetallic compound Ni3(Si,Ti) in sodium chloride solutions

The pitting corrosion of intermetallic compound Ni₃(Si,Ti) was investigated as functions of test temperature and chloride concentration in sodium chloride solutions by using a potential step method. In addition, the pitting corrosion of solution-annealed austenitic stainless steel type 304 and pure nickel was also studied under the same experimental condition for comparison. The pitting potential obtained for the intermetallic compound decreased with increasing chloride concentration and test temperature. A critical chloride concentration below which no pitting corrosion took place was found to exist and to decrease with increasing test temperature. The specific pitting potential at the critical chloride concentration also decreased with increasing test temperature. In addition, the pitting potential at various constant chloride concentrations above the critical chloride concentration decreased with increasing test temperature. The pitting potential of Ni₃(Si,Ti) was higher than pure nickel, but lower than that of type 304.     

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.     

Nondestructive analysis of pitting corrosion characteristics on EN AW-2024-T3 using 3D optical pattern profilometry

High-strength age-hardenable aluminium alloys are susceptible to localised corrosion. It is vital to monitor the evolution of the corrosion depth in order to prevent a critical degradation of the mechanical properties. This study presents the application of 3D optical pattern profilometry for the analysis of the pitting corrosion behaviour of the aluminium alloy EN AW-2024-T3. Therefore, measurements were conducted using a 1?M NaCl solution at different exposure times. The measurements are compared to the results of optical microscopy investigations of metallographic specimens as well as laser scanning microscopy measurements. In immersion bath tests, the 3D pattern profilometry shows a high measurement accuracy of the pitting corrosion. Regarding the pit characteristics, corroded metal sheets exhibit an increase in the pit depth, volume and area with an increasing exposure time of up to 312?h and then decrease. Moreover, a higher increase in the width in rolling direction than perpendicular to it is noticeable.     

Corrosion behavior of Cu–Al–Be shape memory alloys with different compositions and microstructures

The corrosion behavior of Cu–Al–Be shape memory alloys with different microstructures and Be content in a 3.5% NaCl solution was studied by weight loss, cyclic anodic polarization and chronoamperometric measurements. The beryllium has a beneficial effect in β alloys. A pitting potential of −100 mV/SCE was found by anodic polarization tests for all the studied alloys, corresponding to the formation of pits produced by severe dealuminization. Samples with precipitates were more susceptible to pit formation. The corrosion behavior is strongly affected by the alloy microstructural conditions, and the β samples present higher pitting resistance and repassivation ability.     

Corrosion behaviour of copper under chloride-containing thin electrolyte layer

The corrosion behaviour of copper under chloride-containing thin electrolyte layers (TEL) was investigated using electrochemical impedance spectroscopy (EIS), cathodic polarization, linear polarization, SEM/EDS and XRD. The results indicate that the copper corrosion rate increases as TEL thickness decreases during the initial stages. After 192 h of immersion, the corrosion rate of copper under TEL in this order: 300 > 402 > 199 > bulk solution > 101 μm. The corrosion behaviour is uniform under TEL, and pitting is the primary corrosion type in the bulk solution. A corrosion model of the behaviour of copper under chloride-containing TEL is proposed.     

The effect of annealing on the corrosion behaviour of 444 stainless steel for drinking water applications

In this study, the corrosion behaviour of annealed and not annealed AISI 444 ferritic stainless steel in tap water with and without addition of selected concentrations of chloride ions was investigated. Cyclic potentiodynamic macro (large area) and micro (small area) polarization measurements (CPP), salt spray test, SEM and EDS analysis were employed to evaluate the pitting and crevice corrosion susceptibility of annealed and not annealed AISI 444. The results obtained indicate that annealing does not improve the resistance to pitting and crevice corrosion. Moreover, micro CPP indicates local susceptibility to pitting on both annealed and not annealed materials; such susceptibility was not evident from macropolarization tests.     

Protective coating on Mg AZ91D alloy - The effect of electroless nickel (EN) bath stabilizers on corrosion behaviour of Ni-P deposit

The effects of the electroless nickel (EN) bath stabilizers; thiourea (TU) and maleic acid (MA), on the corrosion of the EN coatings on Cu and Mg substrates were investigated in an aggressive oxygenated chloride environment.Corrosion was limited to the external EN layer, and thus, the intermediate Cu layer as well as Mg AZ91D substrate remained intact. On the EN surface, two different types of corrosion morphologies were observed. Specimens prepared with TU showed preferential attack along particle boundaries, while pitting corrosion was observed for specimens prepared either without a stabilizer or with MA. The latter deposits showed higher corrosion resistances due, in part, to the formation of a P-enriched layer on the surface. The poorer corrosion performance of EN specimens prepared with TU was attributed to the presence of the particle boundaries and the trace impurities adsorbed on, or included in, them. The key impurity was sulphur incorporated during formation of deposits in TU-stabilized baths.It was clearly shown that the corrosion behaviour of the EN specimens was predominantly influenced by the morphological and surface compositional aspects of the deposits.     

Corrosion in solar heating systems. II. Corrosion behaviour of AA 6351 in water/glycol solutions

A research was carried out in order to investigate the corrosion behaviour of the metals most commonly used as construction materials for solar absorber plates. With this view, an attempt was made to test the corrosion resistance of the aluminium alloy AA 6351 (nominal composition: 1% Si, 0.6% Mg, 0.3% Mn, the balance Al) towards common uninhibited heat transfer fluids, such as ethylene and propylene glycol/water mixtures. Long time gravimetric tests consisted in up to 60 day exposures of the aluminium specimens to pure, chloride-polluted, or degraded glycol/water solutions, at the temperature of 80°C. The degradation into acidic products, experienced by heat transfer liquids in service, was simulated by keeping the ethylene and propylene glycol/water solutions at their boiling temperature for 30 days, in contact with copper. In glycol/water solutions the presence of chlorides at low concentration (200 ppm) caused the aluminium corrosion rates to increase by more than one order of magnitude, while in degraded solutions, containing 143 or 86 ppm cupric ions, corrosion rates higher than two order of magnitude with respect to pure solutions were obtained. During the gravimetric tests, pitting corrosion was observed in some cases and its extent was rated by evaluating the deepest and the average metal penetration, the pit density and the average pit size. The influence of heat transfer on the alloy AA 6351 corrosion and on the couple copper/AA 6351 efficiency was evaluated by gravimetric and electrochemical tests. Heat transfer through aluminium was found to significantly increase the aluminium alloy pitting potential. On the contrary, it stimulated the aluminium galvanic corrosion, when applied on either aluminium or copper. Under galvanic coupling conditions, the aluminium corrosion rates calculated from the average galvanic currents were a very little contribution to the gravimetric corrosion rates. This demonstrates that in low conductive solutions the risk of matching such dissimilar metals as copper and aluminium does not reside in the galvanic contact itself, but mainly in the mere presence of the noblest metal in the same solution where aluminium is immersed.     

A stochastic analysis of the effect of magnetic field on the pitting corrosion susceptibility of pure magnesium

The effect of magnetic field on the pitting corrosion susceptibility of pure magnesium was investigated by stochastic approaches. Stochastic models had been applied to simulate pitting corrosion as the combination of two physical processes: pit initiation and pit growth. The results revealed that magnetic field increased the pitting corrosion susceptibility of pure magnesium. For the pit initiation process, the presence of magnetic field changed the mechanism of pit initiation from the parallel birth and death stochastic model (B1) to the parallel birth stochastic model (A3). Magnetic field increased the pit generation rate λ while decreased the repassivation rate µ, which indicated that magnetic field accelerated the pit initiation process of pure magnesium. For the pit growth process, magnetic field didn't change the pit growth mechanism, but it could decrease the ability of repassivation of pitting corrosion resulting in a great probability for the stable pitting corrosion to grow up with a higher growth rate and finally develop into larger pit cavity.     

In-situ investigation on the pitting corrosion behavior of friction stir welded joint of AA2024-T3 aluminium alloy

The surface corrosion behavior of an AA2024-T3 aluminium alloy sheet after friction stir welding was investigated by using an “in-situ observation” method. SEM observations showed that the density and degree of the pitting corrosion in the shoulder active zone were slightly larger compared to the other regions on the top surface. The origins of the pitting corrosion were in the regions between the S phase particles and the adjacent aluminium base. The effect of Al-Cu-Fe-Mn-(Si) intermetallic compounds on the pitting corrosion was attributed to their high self-corrosion potential which induced the anodic dissolution of the surrounding aluminium matrix.     

The influence of the cathodic process on the interpretation of electrochemical noise signals arising from pitting corrosion of stainless steels

The use of electrochemical noise (EN) measurements for the investigation and monitoring of corrosion has allowed many interesting advances in the corrosion science in recent years. A special advantage of EN measurements includes the possibility to detect and study the early stages of localized corrosion. Nevertheless, the understanding of the electrochemical information included in the EN signal is actually very limited. The role of the cathodic process on the EN signals remains uncertain and has not been sufficiently investigated to date. Thus, an accurate understanding of the influence of the cathodic process on the EN signal is still lacking. On the basis of different kinetics of the oxygen reduction it was established that the anodic amplitude of transients arising from pitting corrosion on stainless steel can be decreased by the corresponding electron consumption of the cathodic process. Therefore, the stronger the electron consumption, the weaker the anodic amplitude of the EN signal becomes. EN signals arising from pitting corrosion on stainless steel can be measured because the cathodic process is inhibited by the passive layer. This was confirmed by means of EN measurements under cathodic polarisation. Since the cathodic process plays a decisive role on the form of transients arising from pitting corrosion, its influence must be considered in the evaluation and interpretation of the EN signals.     

Corrosion behaviour of aluminium in copper containing environment

Corrosion behaviour of pure aluminium galvanically connected to metallic copper or in the presence of Cu²⁺ ions was investigated by electrochemical measurements in Na₂SO₄ and Na₂SO₄ + NaCl test solutions. It has been found that in aerated Cl⁻ ion containing solutions pitting corrosion of aluminium emerged immediately, while in the absence of oxygen this process was less violent. Effect of passivating pre-treatment of aluminium surface on corrosion behaviour Cu-Al bimetallic system is also demonstrated.     

Combined anodic/cathodic transient currents within nucleating pits on Al–Fe alloy surfaces

Pit nucleation and metastable growth on microelectrodes of aluminium and some Al alloys in chloride solution below the pitting potential are described by recurring current transients. Pit nucleation is a sharp, violent event and is observed repeatedly on all materials tested: pure aluminium, titanium and iron binary aluminium alloys, and alloy 1050A. At the imposed electrode potential, current transients due to pit nucleation recorded for pure aluminium and a solid solution titanium binary alloy are exclusively anodic. Those from alloys containing iron intermetallics sometimes exhibit both anodic and cathodic wings. The cathodic wing is due to transient hydrogen evolution at sites which border iron-rich intermetallic particles: these are preferred pit nucleation sites.     

Effect of hydrostatic pressure on the corrosion behaviour of Ni-Cr-Mo-V high strength steel

Effect of hydrostatic pressure on the corrosion behaviour of Ni-Cr-Mo-V high strength steel was investigated by electrochemical measurements and SEM observation. The electrochemical noise (EN) data was analyzed based on non-linear dynamic theory. The experimental results revealed that hydrostatic pressure decreased the corrosion resistance of Ni-Cr-Mo-V steel and the corrosion at high hydrostatic pressure was more uniform due to the higher initiation rate and lower growth probability of metastable pitting.