Participation of the dissolved O2 in the passive layer formation on Zn surface in neutral media

The composition of the passive layers formed on Zn electrode in naturally aerated and de-aerated 0.1 M KClO₄ solution were studied using X-ray photoelectron spectroscopic measurements (XPS). A correlation between the presence of dissolved O₂ and the formation of an interior passive layer was carried out. Librated Cl⁻ from the perchlorate reduction reaction was detected in its solutions during Zn electrode polarization. The librated Cl⁻ concentration reached its maximum value at −1.4 V. Moreover, in the studied potential range the perchlorate reduction rate increases in absence of dissolved oxygen. Chrono-amperometry and electrochemical impedance spectroscopy (EIS) were performed for the stationary and the rotating disc Zn electrodes in naturally aerated and de-aerated 0.1 M KClO₄ solution. EIS technique showed a change in the electrode impedance with the experimental conditions as a result of changing the reactions occurring in the electrode vicinity. The obtained data were fitted to three different equivalent circuits depending on the electrode potential. The protective nature of the passive layers formed in different experimental conditions was found to decrease with rotating the electrode and de-aerating the solution.     

钛纳米聚合物涂料在NaCl溶液中的电化学阻抗谱

采用电化学阻抗谱方法对钛纳米聚合物涂料的防腐性能进行了研究,并通过与环氧树脂清漆、环氧玻璃鳞片涂料的对比,说明钛纳米聚合物涂料的防腐性能显著优于上述两种涂料的防腐性能。     

Influence of the solution cation mobility on the water uptake estimation of PVC Plastisol freestanding films by EIS

In this work, the influence of the outer solution cation mobility on the electrochemical behaviour of PVC Plastisol freestanding films was studied. For that purpose, the paint films were immersed in 0.5 M and 0.05 M chloride solutions with different cations (Na⁺, K⁺, Cs⁺). The electrochemical impedance spectroscopy (EIS) was the technique chosen for this study and estimated values of film capacitance and resistance were calculated.

For PVC Plastisol films, it was observed that the ion diffusion depends on the outer solution concentration. To explain such results different mechanisms for the ionic diffusion were considered. For higher concentration solutions the ions of the outer solution must diffuse into the film, while for lower concentration solutions the dissolution inside the film occurs followed by ionic diffusion from the film to the outer solution.

The water uptake was determined by EIS and gravimetry techniques. The Brasher and Kingsbury (BK) and the low frequency solution (LF) models were used to estimate this parameter by the EIS technique. A direct dependency between water uptake and solution concentration was obtained by this technique, while by gravimetry an inverse relation was obtained. However, the LF model presented water uptake values better correlated with the gravimetric ones comparatively to the BK equation. For the more concentrated solutions, the cation mobility influenced the water uptake estimated by EIS, whereas, such dependency was not observed with the gravimetric technique.

The results obtained in this work suggest that the outer solution resistivity and consequently the film resistance influence the water uptake measurements and should take part in any improved model used for water uptake determination.     

An electrochemical and microstructural characterization of steel-mortar admixed with corrosion inhibitors

The present research brings new insights on the role of admixed corrosion inhibitors in the processes of cement hydration and rebar corrosion. The admixing of NaCl and the corrosion inhibitors in fresh mortar was found to alter the morphology and microstructure of the hardened mortar at the steel-mortar interfacial region. The admixing of the inhibitors increased the risk of carbonation of cement hydrates at the steel-mortar interfacial region, but partially displaced chloride ions. Chloride and the admixed inhibitors facilitated the formation of different cement hydrates and affected chloride binding at the steel-mortar interfacial region. The admixing of all three inhibitors was found to increase the polarization resistance of steel, indicating reduced corrosion rate of the steel over 48-day exposures to salt ponding.     

碳钢和纯铜在试验土壤中的腐蚀研究

采用交流阻抗谱和极化曲线测试技术,研究了碳钢和纯铜在4种不同土壤介质中的腐蚀规律．实验结果表明,土壤配制液对碳钢和铜电极的侵蚀性与土壤溶液的pH值有较大关系．     

Corrosion processes and their influence on the magnetic flux density of FeNbCuSiB alloys

This paper describes the effect of corrosion process in the magnetic flux density of FeNbCuSiB alloys and correlates with the Si content in the alloys and in the surface oxide layer after a corrosion process. The corrosion resistance of FeNbCuSiB alloys was studied by ordinary weight loss tests, the potentiodynamic polarization technique and spectroscopy impedance. The photoelectron spectroscopy was used in order to identify the compositional changes in the surface oxide layer. Two alloy compositions, Fe_77.5Cu₁Nb₃Si_2.5B₁₆ and Fe₇₃Cu₁Nb₃Si_16.5B_6.5, with different Si content were analyzed in two different conditions, amorphous and crystalline states, respectively. The Fe_77.5Cu₁Nb₃Si_2.5B₁₆ alloy displayed lower corrosion resistance than the Fe₇₃Cu₁Nb₃Si_16.5B_6.5 alloy. The increase of the Si amount in the alloy composition results in an improvement in the corrosion resistance. The enrichment of the Si content on the surface oxide layer was found to be responsible for the improved corrosion resistance. Losses in magnetic properties depend not only on the Si content but also on the structural state.     

非晶合金Mg_(65)Y_(10)Cu_(25)在3.5%NaCl溶液中的腐蚀行为

利用电化学极化曲线方法、交流阻抗 (EIS)技术和扫描电子显微镜 (SEM )研究了Mg65Y10 Cu2 5非晶及相应的晶化合金在 3 5 %NaCl溶液中的腐蚀行为。极化曲线测试结果表明 ,非晶合金Mg65Y10 Cu2 5在NaCl溶液中为活性溶解 ,腐蚀反应由阴极反应和阳极反应共同控制。EIS测试表明 ,随着浸泡时间延长 ,非晶合金耐蚀性下降 ,EIS由 3个时间常数变为 2个时间常数。SEM测试表明 ,非晶合金经过 2 4h浸泡后 ,表面发生了极为不均匀的腐蚀 ;EDAX能谱表明 ,非晶合金经过浸泡后 ,表面成分发生了较大变化 ,含镁量减少 ,表面出现了浓度分布不均匀的氧元素。晶化后Mg65Y10 Cu2 5合金的耐蚀性略有提高。探讨了非晶合金在 3 5 %NaCl溶液中的腐蚀机理     

Sintering atmosphere and temperature effects on hydroxyapatite coated type 316L stainless steel

Electrophoretically deposited hydroxyapatite (HAP) coatings on type 316L SS was developed at the optimum coating parameters of 60 V and 3 min. Sintering of the coating enhances the metal-ceramic bond strength, but HAP structure is sensitive to temperature as it decomposes to other calcium phosphate phases. Sintering of HAP coatings in air at 900 °C for 1 h indicate the formation of a composite surface containing oxides of the alloy and decomposition products of HAP, mainly tricalcium phosphate. Open circuit potential-time measurements, potentiodynamic cyclic polarisation and electrochemical impedance experiments performed in Ringer’s solution indicate that the corrosion performance of HAP coatings were severely affected by the sintering atmosphere and temperature. Higher capacitance and low polarisation resistance values obtained from electrochemical impedance spectroscopic studies further indicate that the coatings are more prone to dissolution on comparison with the pristine type 316L SS. The sintering of the coatings in vacuum at 600, 800 and 900 °C for 1 h did not alter the phase purity of the coatings, and shifted the electrochemical parameters towards noble direction. Sintering of the coatings in vacuum lead to the formation of an adherent, stoichiometric HAP coating with enhanced corrosion resistance.     

X-ray photoelectron spectroscopy study of the corrosion behaviour of galvanised steel implanted with rare earths

The present paper studies the effect of ion implantation of 2 × 10¹⁶ ions/cm² of Ce⁺ and 2 × 10¹⁶ ions/cm² of La⁺ at 150 keV on the corrosion behaviour of hot-dip galvanised steel. After implantation, galvanised steel was characterised by means of XPS previous to and following immersion in the medium. The results revealed incorporation of cerium and lanthanum on the surface as Ce₂O₃ and La₂O₃, respectively. Electrochemical impedance spectroscopy was carried out in order to evaluate its corrosion behaviour in 0.6 M NaCl during 1 month of immersion. The corrosion resistance was improved by an increase in the charge transfer resistance of the implanted specimens in the medium. This effect could be associated with changes in the morphology/microstructure of the corrosion products layer rather than in its composition variations.     

Surface characterization and corrosion behavior of 70/30 Cu-Ni alloy in pristine and sulfide-containing simulated seawater

The corrosion behavior of the 70/30 Cu-Ni alloy in stagnant, aerated pristine and sulfide-containing simulated seawater as a function of exposure time was investigated with polarization curve measurement and electrochemical impedance spectroscopy (EIS). It was demonstrated that the compact protective oxide film formed on the 70/30 Cu-Ni alloy resulted in the decrease of corrosion rate in aerated pristine seawater; while the corrosion rate of 70/30 Cu-Ni alloy in aerated sulfide-containing seawater increased dramatically due to the catalysis of the sulfide ions or sulfide scale for both the cathodic and anodic reactions. The impedance spectra and the corresponding equivalent circuits confirmed that a duplex layer of a surface film was formed on the 70/30 Cu-Ni alloy in aerated pristine seawater after a period of time and that the inner layer was responsible for the good resistance of the alloy; while only a porous and non-protective corrosion product layer formed on the 70/30 Cu-Ni alloy in aerated sulfide-containing seawater, which made small values of charge transfer resistance (R_ct) to last for a abnormally long time by interfering with the growth of the protective oxide film. The composition of the surface film on the alloy in pristine and sulfide-containing seawater for different exposure times were investigated thoroughly by XPS. It was found that the duplex corrosion product layer formed on the alloy in pristine seawater was composed of an inner Cu₂O and an outer CuO layer. The porous and non-protective corrosion product layer formed on the alloy in aerated sulfide-containing seawater was a mixture of CuCl, Cu₂S, NiS, Cu₂O and NiO with trace amounts of CuO and Ni(OH)₂ and that the most significant component was Cu₂S. In addition, SEM was used to analyze the topography of the 70/30 Cu-Ni alloy in both solutions after different exposure times.