Effect of chromium content and sweep rate on passive film growth on iron-chromium alloys studied by EQCM and XPS

Growth of passive films on Cr and Fe-Cr alloys with Cr concentrations ranging from 15% to 54% was studied in situ with the electrochemical quartz crystal microbalance (EQCM). Mass change and current transients were measured as the response to a potential change in the passive region from 0 to 800 mV (SHE) in a pH 1.5 sulfate electrolyte. From these measurements, the thickness change as well as integral and differential growth fractions were calculated. The growth fraction expresses the fraction of oxidized metal that remains in the film. It was found that higher Cr contents gave thicker films and an increase in the growth fraction. The thickness change curves were compared to film growth models assuming rate control at either a film interface or in the film itself through high field conductivity. The integral growth fraction for the potential change experiment was found to vary approximately linearly with the Cr bulk composition. The fraction of dissolved Cr calculated from EQCM data matched well with previous solution analysis results.     

Effects of nitric acid passivation on the pitting resistance of 316 stainless steel

Samples of 316 stainless steel have been subjected to passivation treatments at ambient temperature for 1 h in solutions of up to 50 wt% nitric acid. Pitting potentials of the treated samples were measured in 1 M NaCl at 70°C and were shown to vary with the concentration of the pre-treatment; increasing with concentration up to 25 wt% and then decreasing as the acid concentration was further increased. The corrosion potential reached during the passivation treatment increased with acid concentration, such that the highest measured pitting potential was associated with a final passivation potential of 300–400 mV versus SCE. MnS inclusions were at least partially removed by treatment with any nitric acid concentration, whilst chromium enrichment of the film reached a peak value for an acid concentration of 25 wt%. The rate of metastable pitting was also found to vary with the concentration of the acid used in the passivation treatment, as did the probability of a metastable pit becoming stable. A probabilistic pitting model suggests that acid treatment reduces the number of possible pit initiation sites at low potentials, but the most dangerous sites in corrosion terms are also the most difficult to remove by acid treatment.     

Effects of an applied magnetic field on the dissolution and passivation of iron in sulphuric acid

The effects of an applied magnetic field (MF) on the electrochemical state, anodic dissolution and passivation of iron in sulphuric acid solution were studied by potentiodynamic scanning polarisation measurements, potentiostatic polarisation measurements and scanning electron microscopy observation. The magnetic field reduced the fractional surface film coverage on the electrode by enhancing the film dissolution process. This made the electrode prone to active dissolution. With increasing applied potentials the magnetic field accelerated the anodic dissolution at relatively low potentials, changed the oscillation or passivation to permanent active dissolution at intermediate potentials, and maintained the passive state at high potentials. Potentials for the onset of passivation moved in the noble direction when the magnetic field was imposed. An electrode kinetics formulation for the effects of the magnetic field on the dissolution and passivation is proposed. In the presence of a magnetic field and at specific anodic potentials, scalloping occurred due to accelerated localized dissolution. The scalloping areas were on both sides of the electrode and oriented parallel to the direction of the earth’s gravitation field. The ratios of the scalloping area caused by a 0.4 T magnetic field on the whole electrode surface were 0.69 (at 200 mV), 0.66 (at 350 mV) and 0.75 (at 400 mV), respectively. In contrast, uniform electrode surfaces were observed at these anodic potentials in the absence of the magnetic field. Uneven dissolution of iron in the presence of a magnetic field was related to the relative configuration between the magnetic field direction and the electrode surface and also to the special concentration gradient of reactive species at the electrode circumferential area.     

The transpassive dissolution mechanism of highly alloyed stainless steels: I. Experimental results and modelling procedure

The transpassive dissolution of austenitic stainless steels (AISI 316L, AISI 904L, 254SMO and 654SMO) in a 0.5 M sulphate solution with pH 2 was studied by conventional and rotating ring-disc voltammetry, as well as electrochemical impedance spectroscopy. The main process in the transpassive potential region was found to be the release of soluble Cr(VI), while small amounts of lower-valency Cr or Mo species are released as well. Secondary passivation readily occurs for AISI 316L, whereas the remaining highly alloyed steels dissolve at high current densities in the whole potential range studied. The dissolution rate was found to increase in the order AISI 904L<254SMO<654SMO. Thus it can be correlated to the increase in the Cr and especially Mo content of the steel substrate. The impedance spectra contain contributions from the transpassive dissolution of Cr and secondary passivation, probably due to enrichment of Fe in the outermost layer of the surface film. A kinetic model of the process is proposed, including a two-step transpassive dissolution of Cr via a Cr(VI) intermediate and the dissolution of Fe(III) through the anodic film. The model was found to be in quantitative agreement with steady state current vs. potential curves and electrochemical impedance spectra. The kinetic parameters of transpassive dissolution were determined and the relevance of their values is discussed.     

Effect of selective dissolution on fatigue crack initiation in 2205 duplex stainless steel

The effect of selective dissolution on fatigue crack initiation of 2205 duplex stainless steel (DSS) was investigated in this study. In mixed sulfuric and hydrochloric acid aqueous solution, there existed two distinctly separated anodic peaks in the active-to-passive transition region of the polarization curve. Either ferritic or austenitic phase was selectively dissolved at each characteristic anodic peak potential. Under sinusoidal cyclic loading condition, however, selective dissolution did not assist fatigue crack initiation instead resulting in the elimination of stress concentration site in the selectively dissolving phase. As a consequence, under selective dissolution condition, fatigue crack initiated in the phase while its dissolution rate was lower with respect to the other constituent phase in the duplex stainless steel. The microstructural evolution of the corrosion fatigue crack initiation in 2205 DSS in the mixed sulfuric and hydrochloric acid solution is highlighted in this investigation.     

Passivation of Fe-Cr alloys studied with ICP-AES and EQCM

The response of sputter deposited Fe-15Cr and Fe-25Cr alloys to a rapid potential increase in the passive region was studied using two in situ methods: electrochemical quartz crystal microbalance and inductive coupled plasma-atomic emission spectroscopy (ICP-AES). Both methods indicated an increase in the dissolution rate of iron following the potential change; the total amount of material dissolved being higher for the Fe-15Cr alloy. For both alloys, about 10% of the total dissolved material was Cr. This result compared well with experiments on a 430 stainless steel. ICP-AES is shown to be useful for the in situ determination of partial currents of metal dissolution using solution analysis in a flow cell.     

An atomic emission spectroelectrochemical study of passive film formation and dissolution on galvanized steel treated with silicate conversion coatings

The effect of a silicate conversion coating, which was applied on electrogalvanized steel (EG) and hot dip galvanized steel (HDG), on zinc passivation and dissolution is investigated by atomic emission spectroelectrochemistry (AESEC) using anodic/cathodic cycles in a neutral borate buffer solution. We are able to decompose the total zinc oxidation rate into a soluble (dissolution) and insoluble (passivation) component. It is found that the silicate conversion coating reduces the soluble component with no measurable effect on the insoluble component. The results imply that zinc passive film formation occurs unhindered underneath the silicate film but the film effectively blocks zinc dissolution.     

Corrosion modelling of austenitic steel in molten sulphate deposit

A new explanation of a corrosion test of austenitic steel AISI 316 by Hendry and Lees is presented. A mechanism controlled by the complex alkali iron trisulphate formation reaction is proposed. An attempt has been made to evaluate the equilibrium constant and the rate coefficient of the controlling reaction on basis of the Hendry and Lees experiment. The model describes quantitatively the rate of steel sample corrosion in molten sulphates at 600 °C and its slow down to almost zero as a consequence of the chemical equilibrium state instead of resolidification of the molten sulphates solution.     

The transpassive dissolution mechanism of highly alloyed stainless steels: II. Effect of pH and solution anion on the kinetics

The transpassive dissolution of austenitic stainless steels (AISI 316L, AISI 904L, 254SMO and 654SMO) in a 0.5 M sulphate solution with pH 2 was studied by conventional and rotating ring–disc voltammetry, as well as electrochemical impedance spectroscopy. The main process in the transpassive potential region was found to be the release of soluble Cr(VI), while small amounts of lower-valency Cr or Mo species are released as well. Secondary passivation readily occurs for AISI 316L, whereas the remaining highly alloyed steels dissolve at high current densities in the whole potential range studied. The dissolution rate was found to increase in the order AISI 904L<254SMO<654SMO. Thus it can be correlated to the increase in the Cr and especially Mo content of the steel substrate. The impedance spectra contain contributions from the transpassive dissolution of Cr and secondary passivation, probably due to enrichment of Fe in the outermost layer of the surface film. A kinetic model of the process is proposed, including a two-step transpassive dissolution of Cr via a Cr(VI) intermediate and the dissolution of Fe(III) through the anodic film. The model was found to be in quantitative agreement with steady state current vs. potential curves and electrochemical impedance spectra. The kinetic parameters of transpassive dissolution were determined and the relevance of their values is discussed.     

Distribution and characterization of high temperature air corrosion products on iron-chromium alloys by Raman microscopy

Raman microscopy has been used to study the nature and distribution of corrosion products formed on iron and iron-chromium alloys in air at high temperatures. Fe and Fe-Cr alloys containing 2, 5, 14, and 18% Cr were oxidized at 400, 600, and 850°C for 2 hr, in addition samples of each alloy were oxidized for 24 hr at 400°C to obtain thicker scales at this temperature. The corroded samples showed varying distributions of the oxides Fe₂O₃, Fe₃O₄, Cr₂O₃, and FeCr₂O₄. Fe₂O₃ and Fe₃O₄ were formed exclusively on the pure iron and the 2 and 5% chromium alloys at all temperatures and on the 14% chromium alloy at 400°C. The 14 and 18% Cr alloys formed scales containing Cr₂O₃ and FeCr₂O₄ at the higher temperatures (600 and 850°C). Examples of small regions of Fe₂O₃ being formed within Cr₂O₃-FeCr₂O₄ scales are suggested as possible indications of breakaway corrosion initiation sites.     

选区激光熔化Al-Si合金组织特征及腐蚀行为研究进展

选区激光熔化(selective laser melting, SLM)制备的Al-Si合金在航空航天材料定制化和轻量化的发展中有着巨大潜力。然而,影响SLM成形件寿命的腐蚀行为尚未引起广泛关注。本文结合当前文献报道,根据SLM过程中的凝固特征分析了冶金缺陷和微观组织的形成原因,结合传统铸造Al-Si合金在含氯化合物中的腐蚀机理,进一步论述了SLM制备的Al-Si合金的腐蚀机理,归纳总结了冶金缺陷、微观组织和热处理工艺对于腐蚀行为的影响。发现试样的致密度,表面状态(粗糙度)和共晶Si的含量、形态及分布对腐蚀性能有重要影响。在此基础上,指出了目前SLM工艺下Al-Si合金腐蚀研究中存在的工艺参数不够系统,忽视Mg,Fe等元素的作用,研究手段和范围不够完善等不足以及未来进一步发展的方向。     

A simplified energy-based model for laser welding of ferritic stainless steels in overlap configurations

A theoretical model is developed for predicting the weld shape produced by a Continuous Wave (CW) Nd:YAG laser in a constrained overlap configuration on a ferritic stainless steel, and verified by means of experiments. Tests demonstrate that, as assumed in the modelling phase, penetration depth is linearly dependent on the energy density input, within the hypothesis of conduction dominated welding. Penetration depth determines the weld resistance length at the interface since the weld profile is found to change from approximately semicircular to parabolic when the energy density input is varied in the range from 22 J/mm² to 32 J/mm².     

A comparative study of the corrosion protective properties of chromium and chromium free passivation methods

Commercially available passivation methods for white-rust protection of hot-dip galvanized steel have been investigated. The passivations were either based on trivalent chromium or chromium free. A chromate based conversion coating was used for reference. The treated panels were tested with regard to white rust protection and paintability. The surface chemistry of the conversion coatings was monitored with scanning Auger electron spectroscopy and X-ray photoelectron spectroscopy. Coating thicknesses were measured using Auger electron sputter depth profiling.The passivations were applied with a thickness recommended by the supplier and thus showed large variation. The thickness of the chromium free passivation (Cr-free) is approximately 75 nm. The coating contains the active ions; H₃O⁺, Ti⁴⁺, Mn²⁺, Zn²⁺, PO₄³⁻. The passivation based on trivalent chromium (Cr-III) is approximately 30 nm thick and contains the active ions; H₃O⁺ Cr³⁺, PO₄³⁻, F. The chromate based passivation (Cr-VI) is approximately 5 nm thick and contains the active ions Cr⁶⁺/Cr³⁺, F⁻.The Cr-free and the Cr-III passivations showed similar white rust protection in the corrosion tests. The corrosion resistance was good although it did not fully reach the level of the Cr-VI passivation. The results from the tests of the painted panels showed that the powder paint worked well on all three passivations. The solvent born paint worked best on the passivation based on trivalent chromium. The water born paint showed poor resistance to blistering in the Cleveland humidity test for all three passivations. In this test the passivation with hexavalent chromium showed slightly better results than the chromate free passivations.     

A mixed-conduction model for oxide films on Fe, Cr and Fe-Cr alloys in high-temperature aqueous electrolytes—II. Adaptation and justification of the model

The aim of this two-part work is to propose a model for the corrosion mechanism of ferrous alloys in high-temperature aqueous environments. In this second part, the modifications to the mixed-conduction model (MCM) are discussed on the basis of experimental data presented in the first part for Fe, Cr and two Fe-Cr alloys (12 and 25 wt% Cr) in an aqueous solution at 200 °C. Application of the MCM to fit and predict experimental behaviour both at room temperature and at 200 °C is demonstrated. The major difference between the behaviour of films at room temperature and at 200 °C is that the mobility of ionic defects is much higher at the higher temperature. Estimates show that the ratio of the electronic and ionic diffusion coefficients (D_e/D_i) is of the order of 10⁵ at room temperature and ≈30 at 200 °C for pure Fe. Such a large difference explains the higher growth rate and thickness of films formed on Fe at the higher temperature. It is also in agreement with the higher defect content and lower field strengths in high-temperature films. The application of the MCM to Fe-Cr alloys indicates that the diffusion coefficient of major ionic current carriers is smaller for the alloys than for pure Fe. Alloying with Cr thus lowers the ionic mobility in the passive film on a ferrous alloy also at 200 °C.     

微电化学技术研究双相不锈钢优选腐蚀行为

利用自制的微参比电极定点测量了双相不锈钢中铁素体相与奥氏体相在NaCl水溶液中的腐蚀电位差异,并建立了微电化学测量系统,在HNO3和FeCl3混合溶液中对双相不锈钢铁素体和奥氏体相分别进行电化学行为和腐蚀差异性的研究．实验表明,铁素体相电位比奥氏体相电位低．微电化学技术的研究结果能够解释双相不锈钢宏观的优选腐蚀行为,有利于进一步深化对双相不锈钢的优选腐蚀机理的认识．     

Effect of Alloying Tin on the Corrosion Characteristics of Austenitic Stainless Steel in Sulfuric Acid and Sodium Chloride Solutions

The effect of tin on general and pitting corrosion behaviors of the austenitic stainless steel in sulfuric acid and sodium chloride solutions was investigated by potentiostatic critical pitting temperature, cyclic potentiodynamic polarization, electrochemical impedance spectroscopy, and scanning electron microscopy. The results showed that there is an optimal tin addition which is around(0.062–0.1) wt%, and the general corrosion resistance of B316 LX with 0.08 wt% tin addition in boiling H2SO4 increased remarkably with a corrosion rate of an order of magnitude lower than that of 316 L.Hydrolyzation of tin ions induces more metastable pit occurrence on the material surface. However, the pitting resistance of B316 LX increases because tin oxides improve the density and uniformity of the passive film, and hydroxide and oxide of tin inhabit the process of pit growing. The effect of tin on pitting corrosion process is illustrated schematically.     

The transpassive dissolution mechanism of highly alloyed stainless steels: II. Effect of pH and solution anion on the kinetics

The effect of pH and solution anion on the kinetics of transpassive dissolution of highly alloyed austenitic stainless steels (AISI 904L, 254SMO and 654SMO) was studied by a combination of electrochemical techniques. The experiments were performed in 0.5 M sulphate and 0.5 M chloride solutions, and in an equimolar mixture of the two. The transpassive dissolution was found to start at higher potentials in solutions with higher pH. The rate of transpassive dissolution was shown to decrease with increasing pH and to be the lowest in chloride solutions and the highest in sulphate electrolytes. The steady-state current vs. potential curves and the impedance spectra of the studied materials in the transpassive potential region were found to be consistent with a proposed kinetic model. The model describes the process as dissolution of Cr as Cr(VI) and Fe as Fe(III) through the anodic oxide film via parallel reaction paths. The kinetic parameters of the model in solutions with different pH values and different anions were determined. The role of pH and solution anion in the transpassive dissolution process is discussed in relation to changes induced by these parameters in the composition of the anodic passive film. The factors determining the efficiency of Fe as a secondary passivating agent are also considered.     

Exploring corrosion protection of La-Fe-Si magnetocaloric alloys by passivation

Magnetocaloric La(Fe,Si)₁₃-based alloys are promising materials for magnetic cooling systems but their limited corrosion resistance in water-based heat transfer fluids is critical. The corrosion behavior of as-cast and annealed La-Fe-Si alloy samples was analyzed in comparison to that of La and Fe for evaluation of the impact of alloy chemistry and microstructure. Electrochemical studies were conducted in defined electrolytes starting with aerated distilled water (pH = 6) for assessing the influence of pH value changes and anion contaminations. Specifically, forced flow electrolyte conditions were applied which are closer to operation conditions of real magnetocaloric regenerator beds than stagnant ones. Corroded sample surfaces were analyzed with SEM to assess damage mechanisms. The reactive nature of the alloy constituents determines the high corrosion activity and limited passivation ability of La-Fe-Si alloys. Their exposure to distilled water is particularly detrimental under stagnant conditions as local fluid acidification enhances corrosion processes. These are based on galvanic coupling between the phases with different corrosion activities: La-rich phases > La(Fe,Si)₁₃-based matrix > alpha-Fe(Si). Laminar fluid flow is beneficial for alloy surface passivation. But anion contaminants like sulfate or hydrogen phosphate ions counteract the weak passivity in flowing distilled water. While acidic conditions lead to instable corrosive states, a pH value control of the heat transfer fluid at alkaline conditions is effective for stable passivity of the alloy surface. Also, the applicability of a phosphate conversion coating treatment in 0.15 M NaH₂PO₄ (pH = 4) was evaluated and prospects of this approach are discussed.     

A scalable predictive model and validation for residual stress and distortion in selective laser melting

The unique thermal cycle of rapid melting, solidification, and melt-back in selective laser melting (SLM) induces steep residual stress gradients which lead to part distortion. However, it is extremely difficult to predict residual stress in SLM due to complex multi-physics phenomena and scale-up of millions of laser scans. This paper has developed a geometry scalable predictive model across microscale laser scan, mesoscale layer hatch, and macroscale part build-up to fast predict residual stress in different scanning strategies. The predictions were validated using the L-shaped bar and bridge structures. The geometry scalability law provides an effective tool for optimizing part designs.     

A thermodynamically consistent modelling of stress corrosion tests in elasto-viscoplastic materials

Slow strain rate (SSR) and constant load (CL) tests are the most important techniques used to rank the susceptibility of different materials to stress corrosion cracking in a specific environment. The present paper proposes a thermodynamically consistent phenomenological framework to model both SSR and CL tests of austenitic steels in acid solutions at room temperature. This global one-dimensional approach does not require the computation of local stresses or strains. The goal is to discuss the thermodynamic aspects that allow proposing a one-dimensional model that combine mathematical simplicity with the capability of describing a complex non-linear mechanical behaviour.