Corrosion mechanisms of steel concrete moulds in contact with a demoulding agent studied by EIS and XPS

The behaviour of E24 mild steel was studied by XPS analysis and electrochemical impedance spectroscopy (EIS) in a filtered solution of cement (pH 13), and an alkyl N-aminodiphosphonate aqueous solution called Aquadem^® (7?pH?13). XPS results showed that the corrosion products developed in both media consisted of Fe₂O₃, covered by a very thin layer of goethite. The thickness of this oxide layer was estimated to be 3 nm. XPS analysis also demonstrated the adsorption of Aquadem^® on the outer layer of FeOOH for pH lower than the zero charge pH of goethite (7.55). From XPS and EIS results, physical models of the E24 steel/electrolyte interface are proposed as a function of pH. For 11?pH?13, the steel is covered by a passive film, while for pH?10, pitting corrosion takes place. At pH 7, an additional mass transport phenomenon must be taken into account. The fitting procedure provided values for several physical parameters (electrolyte resistance, passive film resistance), from which the film capacitance and the dielectric constant of the oxide layer were calculated.     

Determination of the zero-charge ph value of a passive iron surface in aqueous solution

Two techniques of measurement of pH₀, which represents the pH of solution at which the total charge of passive metal electrode surface is zero have been developed. The procedures are based on the use of acid-base equilibria between oxide on electrode surface and solution. In the former technique, the pH of the drop of solution that is applied onto the electrode surface is measured. At pH₀, the pH of the drop does not change in time. In the latter procedure, the potential of a passive electrode that is immersed into solutions with various pH values is measured. pH₀ has been measured on a passive iron electrode. The pH₀ values measured by the two procedures are similar. Comparison of pH₀ of passive electrode and various oxides one to determine the composition of a passive film. The introduction of surface-active ions Ba²⁺ and Cl^? to the solution leads to a shift of pH₀ values and electrode potential in opposite directions.     

γ_N相在硼酸缓冲溶液中的腐蚀与钝化性能

采用等离子体源渗氮技术在304L奥氏体不锈钢表面制备高氮面心结构的γ_N相层,利用阳极极化曲线和电化学阻抗谱(EIS)研究γ_N相在pH=8.4硼酸缓冲溶液中的腐蚀行为。结果表明:γ_N相的阳极极化曲线呈现出自钝化-过钝化溶解过程,自腐蚀电位Ecorr较原始不锈钢提高了75mV,维钝电流密度Jp降低近一个数量级,耐蚀性能明显提高。与原始不锈钢钝化膜相比,γ_N相钝化膜的EIS容抗弧直径及|Z|值增大,相位角平台变宽,其电荷转移电阻Rct增至1.064×107Ω·cm2,双电层电容Cdl降至65.4μF/cm2,说明γ_N相钝化膜更致密,表现为近电容特性。随着浸泡时间增加,γ_N相钝化膜的Rct稳定在107Ω·cm2量级,具有良好的稳定性。     

Influence of pH on the passivation behavior of 254SMO stainless steel in 3.5% NaCl solution

The potentiodynamic polarization measurement of 254SMO stainless steel (UNS 31254) was conducted in 3.5% NaCl solutions with pH ranging from 0.1 to 5. The results indicated that this stainless steel offered excellent pitting corrosion resistance in corrosive environments. Further, it also exhibited various features on the polarization curves in different pH solutions. The electrochemical constant-potential passivation treatment performed at different pH followed by XPS analysis revealed that the primary constituents of the outermost layer of the passive films formed in the weak (pH 5) and strong (pH 0.8) acid solutions are iron oxides and Cr₂O₃ and Cr(OH)₃, respectively. Molybdenum oxides, primarily in the six-valence state, existed in the outermost layer of the passive film. Only very weak signals corresponding to that of nickel oxides were detected in the film formed in the weak acid (pH 5) solution. The ICP-MS analyses indicated selective dissolution of a significant amount of Fe and a few Mo and Ni ions during the passivation treatment in the strong acid (pH 0.8) solution. No Cr dissolution was observed; this indicated that the Cr in the film is relatively stable. XPS depth profiling results showed that a similar bilayer-structured film was formed in both the solutions (pH 0.8 and 5); the outer layer of this film is primarily composed of Cr(OH)₃ and Mo(VI), and the inner layer, Cr₂O₃ and Mo(IV). The results of the examinations of passive film formations and dissolution by XPS and ICP-MS were consistent with the polarization curves.     

Depassivation-repassivation behavior of type-312L stainless steel in NaCl solution investigated by the micro-indentation

Repassivation behavior of type-312L stainless steel containing 6% of molybdenum was examined in NaCl solution using in situ micro-indentation technique, together with type-304 and 316L stainless steels. High stability of the passive film formed on the type-312L stainless steel was also examined by depth profiling analysis of passive films using glow discharge optical emission spectroscopy (GDOES). In 0.9 mol dm⁻³ NaCl solution at 296 K the type-304 and 316L stainless steels are passive only up to 0.3 V (SHE), above which pitting corrosion occurs. In contrast, no pitting corrosion occurs on type-312L stainless steel. Despite the significant difference of the pitting corrosion resistance, the repassivation kinetics of the three stainless steels, examined by micro-indentation at 0.3 V (SHE), is similar. The presence of molybdenum in the stainless steel does not influence the repassivation kinetics. The charge required to repassivate the ruptured type-312L stainless steel surface increases approximately linearly with the potential, even though the passivity-maintaining current increased markedly at potentials close to the transpassive region. Repassivation occurs without accompanying significant dissolution of steel, regardless of the stability of passive state. Depth profiling analyses of the passive films on the type-312L stainless steels formed at several potentials revealed that molybdenum species enrich in the outer layer of the passive film, below which chromium-enriched layer is present. The permeation of chloride ions may be impeded by the outer layer containing molybdate, enhancing the resistance against the localized corrosion of the type-312L stainless steel.     

碳化对模拟混凝土孔溶液中HRB335钢腐蚀行为的影响

应用电化学阻抗谱、循环伏安与动电位极化等方法研究了碳化后模拟混凝土孔溶液pH值的变化对钢筋腐蚀电化学行为的影响.结果表明,随着pH值的下降钢筋表面钝化膜的稳定性与耐蚀性不同程度地降低.当模拟液pH值为12.5与11.5时,钝化膜的稳定性处于因pH值降低导致的钝化膜溶解与表面沉积物CaCO3或含钙氧化物CaFe2O4等耐...     

Poly(ortho-ethoxyaniline) in corrosion protection of stainless steel

Corrosion protection of stainless steel (13% Cr) coated with poly(ortho-ethoxyaniline) (POEA) has been investigated. The layers of POEA were synthesised from sulphuric and phosphoric acid solutions by means of cyclic voltammetry. The protecting properties of the layers in supporting electrolytes were investigated by monitoring the open circuit potential (E_oc) vs. time, and by electrochemical impedance spectroscopy (EIS). It was found that polymer layers provide corrosion protection, i.e. they help to stabilise the potential of the metal in the passive potential region. The protective properties of POEA layers have shown to be superior to polyaniline (PANI) layers, which is explained by a denser morphology of POEA. The behaviour of POEA obtained on stainless steel, examined by EIS, is different from the one obtained for POEA on Pt electrode. The registered resistance in the case of POEA on stainless steel represents the charge transfer resistance at polymer/solution interface, i.e. the polymer resistance. These measurements show that a part of the layer is reduced, i.e. that there is an interaction between polymer layer and stainless steel. EIS measurements prove the influence of monomer on stainless steel oxide formation and suggest that polymer is partly incorporated into the oxide film.     

The enhanced passivation of 316L stainless steel in a simulated fuel cell environment by surface plating with palladium

A thin layer of Pd deposition on the surface significantly improves the corrosion resistance of 316L stainless steel in 0.5 mol L⁻¹ H₂SO₄ + 2 ppm F⁻ solution at 80 °C. Compared with the air-formed passive film, the passive film formed in the stainless steel/Pd couple contains more Cr, Cr(OH)₃ and Fe₃O₄ and less point defects, which provides better protection to the stainless steel substrate. The interfacial contact resistance of the stainless steel surface is also decreased. The Pd plated stainless steel is a potential material for bipolar plates in proton exchange membrane (PEM) fuel cells.     

Surface physico-chemistry study of an austenitic stainless steel: Effect of simple cold rolling treatment on surface contamination

The surface physico-chemistry properties of stainless steel and the effects of a cold rolling treatment were investigated. X-ray photoelectron spectroscopy (XPS) analyses were carried out on rolled surfaces at different rates. Thus, by characterizing passive film chemistry and contamination layer, the modifications due to this treatment were quantified, in particular an increase of the ratio (Fe/Cr)_oxide is evidenced with the level of the cold rolling treatment. Moreover, based on an angle resolved analysis, a new model where the contamination layer is represented as isolated parts was developed in order to describe the geometry of this carbon contamination. XPS experiments show an iron enrichment of the passive film during the cold rolling treatment, which seems to be explained by a surface heating during the mechanical treatment. Therefore, the new island model puts in evidence the effects of ageing time and surface condition on the geometry of carbon contamination. Hence, cold rolling increases the thickness and the recovery of carbon contamination on the stainless steel surface.     

18-8不锈钢在含Cl~-介质中钝化膜化学组份的特征

应用 ESCA 和 AES 研究了18-8不锈钢在含 Cl~-介质中,表面阳极钝化膜的化学组份及其深度分布。着重考察了介质中的 Cl~-对钝化膜化学组份的影响,并讨论了 Cl~-在电极表面可能的反应。作者认为介质中的 Cl~-虽可嵌入钝化膜的表面层,但 Cl~-的嵌入并非是导致膜破坏的唯一原因。     

Untersuchungen zum Aktiv/Passiv-Übergang von nichtrostenden Chromnickelstählen in organisch wäßrigen Medien. Teil 3. Resultate der Impedanzmessungen und Passivierungsmodell einer Legierung

Investigations into the active/passive transition of 304 stainless steel in organic media containing water and hydrogen chloride Part 3. Results of the impedance measurements and passivation model of an alloy Steady state polarization curves and electrode impedances were measured during the active/passive transition of type 304 stainless steel in dearated ethanolic solution containing hydrogen chloride and different amounts of water. The passivation potential and the critical current density for passivation strongly depend on the water content of the solution. The impedance measurements in the active/passive transition show the same sequence of diagrams independent of the water content of the solution. They indicate the onset of passivation before the maximum current density and show two time constants related to two different passivating species on the alloy surface. The experimental results were interpreted on the basis of a reaction model with parallel dissolution and passivation mechanism of the iron and the chromium compound of the alloy. The resulting total surface composition (related to the steady-state polarization curves) can be described with a reaction model of iron–the alloy behaviour is that of pure metal. The fundamental passivation reaction is described as a potential dependent equilibrium between adsorbed Me(II)- and passivating Me(III)-hydroxide, water molecules being directly involved in the formation of this primary passivating film. In the case of stainless steel this primary passivating film mainly consists of chromium (III) adsorbates. Finally, a general model for the passivation is proposed: The passivation of a pure metal or of an alloy can be understood as the coupling of the stepwise deprotonation of the water molecules at the interface metal/solution and the formation of a high cation charge density in this adsorbed hydroxide/oxide film to build up the passive layer. The effect of water content, pH, adding of passivating species to the solution or the alloying with chromium on the passivation potential and the critical current density thus can be explained.     

Effect of temperature on anodic behavior of 13Cr martensitic steel in CO2 environment

The corrosion behavior of 13Cr martensitic stainless steel in a CO₂ environment in a stimulated oilfield was studied with potentiodynamic polarization and the impedance spectra technique. The results showed that the microstructure of the surface scale clearly changed with temperature. This decreased the sensitivity of pitting corrosion and increased the tendency toward general (or uniform) corrosion. The capacitance, the charge transfer resistance, and the polarization resistance of the corrosion product scale decrease with increasing temperature from 90 to 120 °C, and thus the corrosion is a thermal activation controlled process. Charge transfer through the scale is difficult and the corrosion is controlled by a diffusion process at a temperature of 150 °C. Resistance charge transfer through the corrosion product layer is higher than that in the passive film.     

Stainless steels: Passive film composition,pitting potentials,and critical chloride content in concrete

Stainless steel reinforcing bars show excellent corrosion resistance in concrete structures exposed to harsh environments. Only a little information on the surface chemistry of these materials in alkaline media is available. This study reports the X-ray photoelectron spectroscopy surface analytical results (thickness, composition of the passive film and of the interface beneath the film) obtained on black steel, FeCr alloys, DIN 1.4301, DIN 1.4462 and the nickel-free DIN 1.4456 after exposure to alkaline solutions simulating concrete. The pitting potentials of the steels could be related to the Cr(III)oxy-hydroxide and Mo(VI) content in the passive film. C_crit, the critical chloride content for corrosion initiation in concrete, necessary for life-time predictions, can be determined only with time-consuming tests, especially for high-alloyed stainless steel. This study reports a correlation between C_crit in concrete (made with CEM II-A/LL and CEM I) and the pitting potential for carbon steel, Fe12%Cr alloy, DIN 1.4301, and DIN 1.4571 stainless steels. This could allow, for the first time, a quantitative estimation of C_crit for stainless steel in concrete based on short-term solution tests.     

轧制纳米块体304不锈钢腐蚀行为的研究Ⅱ钝化膜保护性能

采用动电位极化曲线和Mott-Schottky分析等电化学测试手段,探讨了轧制纳米块体304不锈钢与普通304不锈钢在0.05mol/L H2SO4＋0.05mol/L Na2SO4溶液中钝化膜的保护性能;运用点缺陷（PDM）模型,分析了不同电位下在0.05mol/L H2SO4＋0.25mol/L Na2SO4溶液中两种材料形成钝化膜的半导体性质,阐述了导致两种钝化膜保护性能差异的根本原因.结果表明：两种材料表面钝化膜都具有n型半导体特征,氧空穴作为主要的载流子参与钝化膜的形成和溶解过程;钝化膜中载流子密度与钝化膜的形成电位之间满足幂指数关系,载流子在两种材料表面的钝化膜中的扩散系数非常接近,说明两种钝化膜遵从相似的形成和溶解机制,但轧制纳米块体304不锈钢中的载流子密度小于普通304不锈钢钝化膜中的载流子密度,从而使其钝化膜具有更好的保护性.     

Effects of nitric acid passivation on the corrosion behavior of ZG06Cr13Ni4Mo stainless steel in simulated marine atmosphere

ZG06Cr13Ni4Mo martensitic stainless steel was nitric acid-passivated to improve its corrosion performance. The effects of nitric acid passivation on the surface morphology, chemical composition, electrochemical properties, semiconductor behavior, and long-term corrosion performance of the stainless steel were investigated using various analytical techniques. An in-depth analysis of X-ray photoelectron spectroscopy (XPS) showed that the passive film formed after the acid passivation process showed high thickness and a duplex character as it consisted of a hydroxide layer and an oxide layer. The oxide layer affected the corrosion resistance and thickness of the passive film. The thickness of the passive film was calculated theoretically as well as experimentally by fitting the electrochemical impedance spectroscopy and XPS results. The electrochemical tests revealed that the dramatic increase in the corrosion resistance of the stainless steel after the passivation was due to the formation of a thick, low-disorder passive film rather than Cr enrichment. The removal of inclusions resulted in higher pitting resistance, whereas the increased roughness showed a negative effect on the corrosion behavior of the stainless steel. During the wet–dry cyclic tests, the modification of the passive film was examined. The passivated stainless steel exhibited good corrosion resistance for up to 50 days of exposure in the simulated environment.     

XPS analysis of the passive film formed on austenitic stainless steel coated with conductive polymer

Improvement of the passivation behavior of Type 304 austenitic stainless steel (SS) by coating with conductive polymers (CPs), like polyaniline (PANI) and poly(o-phenylenediamine) (PoPD), followed by exposure in an acid solution has been demonstrated. The passive films formed on SSs (after peeling off the polymer layer) are compared with those formed during anodic polarization under the same exposure condition. The passive films beneath the CPs are thicker and less hydrated than those formed on uncoated stainless steel. The polymer layer enhances the enrichment of chromium and nickel in the entire passive oxide, forming a more protective film than that formed during anodic polarization. The elemental distribution within the passive film is different in the two modes of passivation. The type of the polymer influences on the composition of the passive film. The best passivation is obtained by PoPD, with the passive film resulting in significant resistance of the SS to pitting corrosion in the 3% NaCl solution. The oxide film of this steel is characterized, in its inner and outer layers, by the highest ratio of Cr(OH)₃/Cr₂O₃ and the lowest content of iron species.     

Corrosion and passivation mechanism of chromium diboride coatings on stainless steel

The corrosion resistance of fully crystalline CrB₂ coatings magnetron sputtered onto AISI 316L stainless steel was tested in acidic solutions. CrB₂ coatings showed excellent corrosion protection, but suffered a breakdown when an anodic potential of greater than about +1 V (SHE) was applied to the surface in a 1 M HCl electrolyte. The coating failure at high potentials is attributed to transpassive dissolution of the coating at volume defects, enabling the electrolyte to reach the underlying 316L substrate, resulting in its rapid corrosion and subsequent fracturing of the coating. Electrochemical data and potential-pH (Pourbaix) diagrams, constructed from thermodynamic data, indicate that the corrosion resistance of CrB₂ is due to the formation of a Cr(III) oxide passive film in the absence of activation corrosion.     

Corrosion of hot-rolled 430 stainless steel in HCl-based solution

The mixtures of hydrochloric acid and hydrogen peroxide were employed as the environmental friendly pickling solution for 430 hot-rolled stainless steel in this study. Increase of HCl concentration accelerates the corrosion rate of base metal, however aggravates the intergranular attack in sole hydrochloric acid solution. Addition of oxidant (H₂O₂) boosts the corrosion potential of stainless steel significantly resulting in the change of electrode action. At high oxidant content (0.6?mol?l^?1 H₂O₂), a corrosion product film accumulates onto the surface and the corrosion is then governed by the mass-transport at the film/stainless steel interface. The random dissolving of metal ions because of the film leads to brightening of stainless steel surface and the local corrosion is suppressed.     

High corrosion resistance of austenitic stainless steel alloyed with nitrogen in an acid solution

Passivity of austenitic stainless steel containing nitrogen (ASS N25) was investigated in comparison with AISI 316L in deareated acid solution, pH 0.4. A peculiar nature of the passivation peak in a potentiodynamic curve and the kinetic parameters of formation and growth of the oxide film have been discussed. The electronic-semiconducting properties of the passive films have been correlated with their corrosion resistance. Alloying austenitic stainless steel with nitrogen increases its microstructure homogeneity and decreases the concentration of charge carriers, which beneficially affects the protecting and electronic properties of the passive oxide film.     

Relevance of the cathodic process on the passivation of stainless steels – an approximation to the origin of the rouging phenomenon

Unwanted corrosive phenomena on stainless steel surfaces like rouging had been observed for years occurring at certain service conditions. Rouging consists in the formation of a colored surface film containing mainly iron on metallic surfaces in contact with high‐purity waters. In spite of numerous hypotheses and experimental examinations a clear explanation about the origin of rouging on stainless steels is currently still lacking. Because rouging occurs even at well passivated stainless steel surfaces the origin of this corrosive phenomenon should be related to the weakness of the stability of the passive film. In the present paper electrochemical noise measurements regarding the stability of the passive layer of alloy 904L (1.4539, X1NiCrMoCu25‐20‐5) in high‐purity water at 70 °C depending on the cathodic process are presented. In addition, the importance of the cathodic reaction on the passivation and stability of the passive layer is discussed.