Polyaniline for corrosion prevention of mild steel coupled with copper

Polyaniline emeraldine base/epoxy resin (EB/ER) coating was investigated for corrosion protection of mild steel coupled with copper in 3.5% NaCl solution. EB/ER coating with 5-10 wt% EB had long-term corrosion resistance on both uncoupled steel and copper due to the passivation effect of EB on the metal surfaces. During the 150 immersion days, the impedance at 0.1 Hz for the coating increased in the first 1-40 days and subsequently remained constant above 10⁹ Ω cm², whereas that for pure ER coating fell below 10⁶ Ω cm² after only 30 or 40 days. Immersion tests on coated steel-copper galvanic couple showed that EB/ER coating offered 100 times more protection than ER coating against steel dissolution and coating delamination on copper, which was mainly attributed to the passive metal oxide films formed by EB blocking both the anodic and cathodic reactions. Salt spray tests showed that 100 μm EB/ER coating protected steel-copper couple for at least 2000 h.     

Electrochemical formation of AlN in molten LiCl-KCl-Li3N systems

Electrochemical formation of aluminum nitride was investigated in molten LiCl-KCl-Li₃N systems at 723 K. When Al was anodically polarized at 1.0 V (versus Li⁺/Li), oxidation of nitride ions proceeded to form adsorbed nitrogen atoms, which reacted with the surface to form AlN film. The obtained nitrided film had a thickness of sub-micron order. The obtained nitrided layer consisted of two regions; the outer layer involving AlN and aluminum oxynitride and the inner layer involving metallic Al and AlN. When Al electrode was anodically polarized at 2.0 V, anodic dissolution of Al electrode occurred to give aluminum ions, which reacted with nitride ions in the melt to produce AlN particles (1-5 μm of diameter) of wurtzite structure.     

Zinc-rich powder coatings characterisation in artificial sea water: EIS analysis of the galvanic action

Two zinc-rich powder coatings are applied onto phosphatised steel substrate and are studied using electrochemical impedance spectroscopy (EIS). Measurements are performed before (dry experiment) and during immersion in artificial sea water. Before immersion, EIS spectra show that percolation threshold is not attained for coating A, while coating B presents an effective percolation. In this latter case, and in order to account for the distribution of the zinc particles within the coating described as isolated, semi-isolated and percolant grains, a distributed transmission line model is proposed. When panels are immersed, the model is modified due to the electrolyte penetration through the coating, in particular with the introduction of an ionic resistance. However, it is shown that EIS spectra are not significantly modified when this ionic resistance is changed.     

Aqueous electrochemical intercalation of bromine into graphite fibers

For the first time, graphite fibers have been electrochemically intercalated with Br⁻ that have the same structure and properties as those intercalated from vapor phase Br₂. This was accomplished by intercalating pitch-based Thornel^® K-1100 graphite fibers at low temperature (near 0 °C) and high currents (2 A) for long times (6 h). The mechanism appears to be that Br⁻ is oxidized to aqueous Br₂ which, when sufficient local concentration builds up, intercalates the fiber. This was confirmed by intercalating K-1100 fiber in a saturated aqueous Br₂ solution without passing an electrical current. The applied voltage does apparently lower the activation energy of the reaction as evidenced by the observation that P-120 and P-100 fibers will not intercalate in aqueous Br₂ unless a voltage is applied.     

Electrochemical characterization of 8-hydroxyquinoline-5-sulphonate/aluminium(III) aqueous solutions

8-Hydroxyquinoline-5-sulphonate/Al(III) aqueous solutions were studied both by potentiometric titrations and voltammetric measurements, in order to obtain the number, the stoichiometry and the stability constants of the complexes formed at equilibrium, and to evaluate the redox and (electro)kinetic properties of the free ligand and of the metal/ligand complexes. The complexes formed in 0.2 m (Na)Cl aqueous solution (stability log beta values ± standard deviation) are AlL⁺ (8.95 ± 0.05), AlL₂⁻ (17.43 ± 0.03) and AlL₃³⁻ (24.58 ± 0.05), where “L” denotes the free ligand in the completely deprotonated form (L²⁻, pK_a1 = 3.910 ± 0.008, pK_a2 = 8.319 ± 0.004). AlL₃³⁻ is the predominant Al(III) species in a very wide range of pH, metal and ligand concentrations and metal-to-ligand ratios. The free ligand shows an oxidation wave at 0.62 V versus SCE. The proposed oxidation mechanism includes a first reversible one-electron oxidation of the ligand, followed by a coupling reaction and by a second reversible one-electron oxidation, and finally by a decomposition reaction. The addition of Al(III) lowers the intensity of the oxidation wave due to the formation of the redox-inactive complex AlL₃³⁻. A residual low signal was attributed to the free ligand produced by the complex dissociation, AlL₃³⁻ = AlL₂⁻ + L²⁻. All the kinetic parameters involved in the ligand oxidation and in the complex disruption were calculated on the basis of the agreement between experimental and simulated linear sweep and cyclic voltammetries. Correctness of the mechanisms proposed was further confirmed “a posteriori” by the agreement between potentiometric and linear sweep voltammetric results. The low residual signal observed in the presence of fully formed complex was attributed to the free ligand produced by the complex dissociation, having a kinetic constant estimated 0.2 s⁻¹.     

An in situ Raman study of the intercalation of supercapacitor-type electrolyte into microcrystalline graphite

An initial Raman study on the effects of intercalation for aprotic electrolyte-based electrochemical double-layer capacitors (EDLCs) is reported. In situ Raman microscopy is employed in the study of the electrochemical intercalation of tetraethylammonium (Et₄N⁺) and tetrafluoroborate (BF₄⁻) into and out of microcrystalline graphite. During cyclic voltammetry experiments, the insertion of Et₄N⁺ into graphite for the negative electrode occurs at an onset potential of +1.0 V versus Li/Li⁺. For the positive electrode, BF₄⁻ was shown to intercalate above +4.3 V versus Li/Li⁺. The characteristic G-band doublet peak (E_2g2(i) (1578 cm⁻¹) and E_2g2(b) (1600 cm⁻¹)) showed that various staged compounds were formed in both cases and the return of the single G-band (1578 cm⁻¹) demonstrates that intercalation was fully reversible. The disappearance of the D-band (1329 cm⁻¹) in intercalated graphite is also noted and when the intercalant is removed a more intense D-band reappears, indicating possible lattice damage. For cation intercalation, such irreversible changes of the graphite structure are confirmed by scanning electron microscopy (SEM).     

Corrosion resistance of phosphate coatings obtained by cathodic electrochemical treatment: Role of anode–graphite versus steel

The formation of phosphate coatings by cathodic electrochemical treatment using graphite and steel anodes and evaluation of their corrosion resistance is addressed in this paper. The type of anode used, graphite/steel, has an obvious influence on the composition of the coating, resulting in zinc–zinc phosphate composite coating with graphite anode and zinc–iron alloy–zinc phosphate–zinc–iron phosphate composite coating with steel anode. The corrosion resistance of the coating is found to be a function of the composition of the coating. The deposition of zinc/zinc–iron alloy along with the zinc phosphate/zinc and zinc–iron phosphate using graphite/steel anodes has caused a cathodic shift in the E_corr compared to uncoated mild steel substrates. The i_corr values of these coatings is very high. EIS studies reveal that zinc/zinc–iron alloy dissolution is the predominant reaction during the initial stages of immersion. Subsequently, the formation of zinc and iron corrosion products imparts resistance to the charge transfer process and increases the corrosion resistance with increase in immersion time. The corrosion products formed might consist of oxides and hydroxychlorides of zinc and iron. The study suggests that cathodic electrochemical treatment could be effectively utilized to impart the desirable characteristics of the coating by choosing appropriate anode materials, bath composition and operating conditions.     

Electro-chemical chloride extraction: Influence of C3A of the cement on treatment efficiency

The aim of this study was to clarify whether the C₃A content of cement had a significant effect on electrochemical chloride extraction (ECE) treatment efficiency. It is known that a higher C₃A content in a cement gives it superior chloride complexing ability resulting in the formation of an “insoluble” calcium chloro aluminate compound.ECE was applied using cylindrical specimens made from concrete containing two levels of C₃A (4.3% and 9.05%). Specimens were 5 cm in diameter and 10 cm in height. Steel was placed in the axial direction with an embedded length of 7 cm. These specimens were immersed in an NaCl solution and dried in a stream of air at 40 °C for 10 months. The corrosion was monitored by half-cell potential and polarization resistance measurements. After steel depassivation, ECE was applied for 20, 30, 40 and 50 days using a constant current density of 1 A/m² of steel. At the end of the treatment, the specimens were maintained at 20 °C and 70% RH in order to observe the evolution of the steel (electrochemical measurements).The results show that, after 30 days of treatment, the chloride content remained constant in the specimen. This was probably due to OH⁻ ion formation on the steel. The OH⁻ ions “contribute” to the current transport, decreasing the ECE efficiency. Concerning the C₃A content, ECE efficiency was slightly affected by C₃A because only a part of the bound chloride ions was released. From the point of view of corrosion, half-cell potential showed a shift in the positive direction, indicating little corrosion activity at 20 °C and 70% RH. However, polarization resistance measurements showed that 2 months post treatment corrosion rates were significant, although the corrosion rate decreased from 6 μA/cm² to 2.5 μA/cm².     

Investigation of LSM/8YSZ cathode within an all-ceramic SOFC,Part II: Optimization of performance and co-sinterability

This paper focuses on the cathode and current collector layers of a co-sintered, all-ceramic solid oxide fuel cell (SOFC) concept. Challenges to reach good electrochemical performance have to be overcome, due to more demanding manufacturing conditions, including a relatively high co-sintering temperature. Master sintering curves show that the sintering activity of lanthanum strontium manganite (LSM) is significantly higher than that of 8-mol% yttria stabilized zirconia (8YSZ). By applying a double-layered cathode and a current collector with optimized microstructures the best electrochemical performance of the cathode is 0.26 $\mathrm{\Omega }$cm${}^2$ at 800 $°$C, evaluated from polarization resistances of 8YSZ electrolyte-supported symmetric cells post-sintered at 1150 $°$C $<T<1250$ $°$C. The cathode and current collector materials are adapted to fit the co-sintering process by adjustment of the paste compositions. Half-cells consisting of silicate mechanical support, LSM current collector, LSM mixed with 8YSZ composite cathode and 8YSZ electrolyte are co-sintered porous and defect-free at 1150 $°$C $<T<1250$ $°$C.     

Zinc-rich powder coatings corrosion in sea water: influence of conductive pigments

The effect of addition of conductive pigments like carbon blacks on the corrosion behavior of zinc-rich powder paints coated steel in artificial sea water was investigated. Open circuit potential measurements were used to characterize the cathodic protection ability and duration. Micro-Raman spectroscopy analysis was performed in order to identify the corrosion products and to follow the penetration of the solution inside the coatings.

Two different effects were pointed out: an increase of the porosity induced by carbon addition and a galvanic action between zinc and carbon pigments. The performance of the powder coatings, strongly improved if the carbon amount is sufficient, was compared to the one reported for solvent-based zinc-rich paints.