Passivity arises from spontaneous formation of a thin protective passive film (oxide/hydroxide layer) on the metal surface, and the stability of passive film is of great importance for corrosion resistance. This study investigates the formation, stability, and transpassive dissolution of passive films on two Ni-based alloys, Alloy 625 and Alloy 59, in acidified NaCl solution, by combining in situ electrochemical synchrotron ambient pressure X-ray photoelectron spectroscopy (AP-XPS) with ex situ glow discharge optical emission spectroscopy (GD-OES) and electrochemical testing, as well as TEM and chemical analyses of the electrolyte. The use of these techniques enables a detailed analysis of chemical states of alloying elements and their distribution within passive films. AP-XPS results reveal a Cr-rich oxide in the thin passive film, which also contains Mo-and Nb-oxides enriched in the near-surface region, and a Cr-hydroxide layer on top of the surface. At increased polarization potentials, low valence Mo-and Nb-components are further oxidized to higher valence components. GD-OES results show that, in the transpassive potential region, the oxide film can grow to several tens of nm thick, while the two Ni-base alloys exhibit quite different behavior. For Alloy 625, Cr is depleted, Ni is almost not present, while Mo and Nb are dominant in the thick transpassive oxide film. In contrast, for Alloy 59 (Nb-free alloy), Cr and Mo remain enriched in the near-surface region and near the base metal, and Ni is present but below 10% in the thick transpassive oxide film. Nb in Alloy 625 forms a stable oxide and inhibits transpassive dissolution, thus contributing to corrosion resistance. By elucidating the fundamental mechanisms governing passivity breakdown, this study provides critical insights for the development of advanced Ni-based materials with enhanced corrosion resistance in aggressive environments.

Passivity refers to spontaneous formation of a passive film on the surface of metals. High stability of the passive film on advanced alloys relies on the repassivation ability of the alloys in corrosive environments. Two Ni-base superalloys (Ni-22Cr-9Mo-5Fe-2Nb and Ni-18Cr-3Mo-20Fe-5Nb) are studied to elucidate the mechanism of repassivation through a combination of multimodal in-situ synchrotron X-ray measurements, electrochemical measurements, and first principles calculations. The synchrotron X-ray analyses enabled in-situ probing of the passive film and the hidden subsurface alloy layer. The results reveal chemical and structural evolutions of both the passive film and the underlying subsurface alloy layer under transpassive condition. The first principles calculations demonstrate a crucial role of the subsurface alloy layer in the repassivation of the alloys. Upon passivity breakdown at high electrochemical potentials, the passive film rich in Cr oxide becomes highly defective with vacancies, and metal dissolution leads to generation of vacancies (mainly Ni) in the subsurface alloy layer. This promotes repassivation process by enhanced outward Cr diffusion strengthening the metal bond (more Cr-Ni bonds) in the subsurface alloy layer and, together with the enrichment of high valence Mo- and Nb-oxides in the passive film, lead to repassivation when the high potential is removed, which is different from Fe-rich alloys.

Nano-scale chemical inhomogeneity in surface oxide films formed on a V- and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron- based hard X-ray Photoelectron emission spectroscopy (HAXPES) and microscopy (HAXPEEM) as well as microscopic X-ray absorption spectroscopy (μ-XAS) techniques. The results reveal the inhomogeneity in the oxide films on the micron-sized Cr2N- and VN-type particles, while the inhomogeneity on the martensite matrix phase exists due to localised formation of nano-sized tempering nitride particles at 600 °C. The oxide film formed on Cr2N-type particles is rich in Cr2O3 compared with that on the martensite matrix and VN-type particles. With the increase of tempering temperature, Cr2O3 formation is faster for the oxidation of Cr in the martensite matrix than the oxidation of Cr nitride-rich particles.

The pitting potential, intrinsic surface acidity, point of zero charge of passive film on Al are studied using first-principles calculations to establish their relationships. Influences of alloying elements Zn, Cr, Nb, Si, Mo and Sc on adsorption of NH3 and NaCl, pHpzc of Al2O3 and pitting susceptibility of Al are investigated. The efficiency for enhancing pitting resistance of Al is evaluated, yielding the ratios Si: Zn: Cr: Mo: Nb: Sc = 1.8: − 0.3: 1: 1.9: 1.4: 0.2. A model for the dependence of pitting potential on the concentration of alloying elements in Al alloy matrix is developed, based on effects of alloying elements on the surface charge of passive film. The effects of Sc on pitting potential and pHpzc of Al oxide are predicted based on the calculated results, which are supported by electrochemical measurement, XPS analysis and contact angle titration.

Corrosion results in large costs and environmental impact but can be controlled by thin oxide films that passivate the metal surfaces and hinder further oxidation or dissolution in an aqueous environment. The structure, chemistry, and thickness of these oxide films play a significant role in determining their anti-corrosion properties and the early-stage oxidation dynamics affect the properties of the developed oxide. Here, we use in situ X-ray Photoelectron Spectroscopy (XPS) to study the early-stage oxidation of a Ni-Cr-Mo alloy at room temperature and up to 400 degrees C. Cr and Mo begin to oxidize immediately after exposure to O2, and Cr3+, Mo4+, and Mo6+ oxides are formed. In contrast, Ni does not contribute significantly to the oxide film. A self-limiting oxide thickness, which did not depend on temperature below 400 degrees C, is observed. This is attributed to the consumption of available Cr and Mo near the surface, which results in an enrichment of metallic Ni under the oxide. The self-limited oxide thickness is 6-8 angstrom, which corresponds to 3-4 atomic layers of cations in the oxide. At 400 degrees C, sublimation of Mo6+ oxide is observed, resulting in the formation of an almost pure layer of Cr2O3 on the alloy surface. Lastly, a mechanism is presented that explains the formation of the bi-layer oxide structure observed for Ni-Cr-Mo alloys, which involves the enhanced migration of hexavalent Mo ions in the electric field, which drives mass transport during oxidation according to both the Cabrera Mott model and the Point Defect Model.

Corrosion causes significant challenges in industrial settings, leading to economic losses and safety concerns. Previously, we developed a lignin-polydimethylsiloxane (lignin-PDMS) coating that exhibited high corrosion resistance. However, the adhesion of the developed lignin-PDMS coating to carbon steel was limited, affecting its overall performance. To address this, we incorporated dopamine (DOPA), known for its strong adhesive properties, as a pre-treatment before applying the coating. It was found that the adhesion and corrosion resistance of lignin-PDMS coated steel could be improved by adjusting the pH value of the DOPA solution. The steel treated with pH 4.5 DOPA solution showed two times higher adhesion strength to the coating than non-treated steel. After the DOPA treatment, the coating can maintain high barrier property for at least 3 months in 1 M NaCl solution, which is even better than commercial gelcoat, demonstrating super corrosion protection. Quartz Crystal Microbalance with Dissipation (QCM-D) and X-ray Photoelectron Spectroscopy (XPS) analyses confirmed the DOPA deposition on the steel surface. Our findings show that the DOPA-lignin-PDMS system is an environmentally friendly and efficient solution for enhancing the durability of steels in corrosive environments.

Effect of tempering temperature on the composition of the passive film of a martensitic tool alloy was studied by synchrotron-based hard/soft X-ray photoelectron spectroscopy and electrochemical analyses. The contents of Cr and Mo in the passive film are affected by precipitation of tempering carbides. Increase of tempering temperature from 200 to 525°C leads to enhanced formation of Cr/Mo-rich tempering carbides and Cr depletion. Tempering at 525°C results in a Cr content < 11 at% in the underlying metallic layer and formation of a Cr-deficient defective passive film, and thus loss of passivity for the tool alloy in corrosive conditions.

Surface films formed on pre-oxidized copper in anoxic simulated groundwater with sulphide were characterized by field emission gun scanning electron microscopy (FEG-SEM), Fourier transform infrared spectroscopy (FT-IR), open circuit potential (OCP) measurements, and via analysing the water chemistry and weight changes in the specimens. Additionally, films developed under identical conditions on pre-oxidized and ground copper specimens were characterized by glow discharge optical emission spectroscopy (GDOES). The results revealed that the sulphide content in the groundwater significantly influences the morphology, composition and thickness of the surface film. The build-up of Cu2S was evidenced at the sulphide contents of 32 mg/L and 320 mg/L. GDOES depth profiling revealed that sulphur and oxygen coexisted in the film all through its thickness, yet the surface was essentially rich in sulphur. The results from characterization are presented in detail in this paper and discussed from the perspective of capabilities of the used methods.

The reformation and characterisation of the passive film formed on ultra-thin 316 L after hydrogen charging is investigated by combining EBSD, TMDS, XRD, Synchrotron-based XPS, and electrochemical experiments. The results show that ultra-thin foil reforms a passive film after 12 h of hydrogen release in NaCl solution. The reformed passive film is half the thickness of the as-received passive film and is dominated by Cr oxides/hydroxides. The lattice extension caused by residual hydrogen accelerates Cr migration to form Cr2O3; while the diffusible hydrogen occupies the cation vacancies and results in high defect density for the reformed passive film within 12 h.

Ambient Pressure X-ray Photoelectron Spectroscopy combined with an electrochemical setup is used to study, in situ, the electrochemical oxide growth on an in-dustrial Ni-Cr-Mo alloy. The native oxide film was characterized in vacuum and in water vapor at 17 mbar, and was found to be 11.4 & ANGS; thick and rich in Cr3+. In 0.1 M NaCl electrolyte, anodic growth of the oxide film at potentials up to 700 mV vs Ag/AgCl nearly doubled the thickness of the oxide film. Moreover, a transformation of the oxide composition occurred, as the oxide became enriched in Mo6+ with a chemical fingerprint more like that of pure MoO3. Both thermodynamics and kinetics of the oxidation of the alloying elements dictate the oxide film growth and composition. Furthermore, we develop the quantitative analysis of oxide composition and thickness to take into account the attenuation through the liquid water and the water vapor atmosphere. Finally, we discuss the differences between ex situ, UHV, in situ, and operando measurements. Our approach is robust, fast, simple, and suitable for systematically probing metal surfaces after aqueous exposure and electro-chemical polarization, which promises wide applications for studies of solid-liquid interfaces in corrosion, batteries, fuel cells, and electrocatalysis.