Passive Film Research Articles

Tailoring surface properties and corrosion resistance of laser shock peened Ti6Al4V alloy by low-temperature annealing

The present study examined the effects of laser shock peening (LSP) and low-temperature annealing after LSP (LSPA) on the corrosion resistance of the Ti6Al4V alloy. The high density of dislocations in the LSP samples contributes to the rapid formation of a TiO₂ passive film during the electrochemical corrosion process. In this study, low temperature annealing was employed to further improve the corrosion resistance. The results indicated that the corrosion resistance of the LSPA samples was significantly improved compared to that of the LSP-treated samples. The LSPA treatment facilitated the pre-generation of a dense TiO2 passive film on the alloy surface via oxidation, reduced corrosion rate, inhibited the penetration of dissolved oxygen and ions present in the sodium chloride solution into the alloy surface. Meanwhile, low-temperature annealing could rearrange and annihilate dislocations, creating subgrains and relaxing non-equilibrium grain boundaries induced by deformation. This process reduced active sites and grain boundary energy, ultimately improving the corrosion resistance of the Ti6Al4V alloy.

Semiconductive Tendency of the Passive Film Formed on Super Austenitic Stainless Steel SR-50A in Acidic or Alkaline Chloride Solutions

Stainless steel is widely used in various industrial fields due to its excellent corrosion resistance and mechanical properties. The key to this corrosion resistance is the thin passive film that naturally forms on the metal surface. Passive films are characterized by oxide film theory and adsorption theory, each uniquely explaining the structure and mechanism of the protective film on the metal surface. Research on the semiconductive properties of passive films on stainless steel offers diverse viewpoints, classifying theories into the point defect model and the bipolar fixed charge-induced passivity. Specific changes in passive film attributes that lead to degradation, however, are not fully understood. In this study, we analyzed the inner and outer layers of the passive film on super austenitic stainless steel SR-50A under various conditions in acidic and alkaline chloride environments. The interpretations of these results were based on the point defect model and the bipolar model for the passivation mechanism, and correlations between p-type and n-type semiconductor properties and passivation behavior were examined. The surface of the stainless steel forms a passive film comprising two layers with p-type and n-type semiconductive properties, independent of the pH of the solutions. The corrosion resistance increases as the p-type and n-type semiconductive tendencies become more balanced, consequently enhancing the properties of the passive film.

Passivation characteristics and corrosion behavior of S32202 duplex stainless steel in different temperatures polluted phosphoric acid

The passivation characteristics of S32202 duplex stainless steel in different temperatures polluted phosphoric acid were studied by electrochemical technology and X-ray photoelectron spectroscopy, and its corrosion behavior was studied through immersion corrosion and electrochemical corrosion. The results indicate that as the temperature increases, the open-circuit potential of the sample in polluted phosphoric acid moves forward, and the surface exhibits a rapid passivation process. The main phases of the passivation film are Fe2O3, Fe3O4, Cr2O3, Cr(OH)3, and corresponding phosphates and polyphosphates. The passivation film of the sample in polluted phosphoric acid exhibits n-p-n composite semiconductor properties. As the temperature increases, the electron density and number of defects in the passivation film increase, and the vulnerability of the passivation film increases. The increase in temperature promotes the formation of a porous thick film. The corrosion types of the sample in polluted phosphoric acid are total corrosion, phase boundary corrosion, and intergranular corrosion, accompanied by pitting corrosion in local areas. The corrosion current density and passivation current density of the sample gradually increase with increasing temperature, while the counter-passivation potential and passivation index decrease, the density and protective properties of the passivation film decrease. The doping of phosphate can alleviate the dissolution process of metals, but the increase in temperature increases the solution ionic activity and accelerates the rate of charge transfer at the interface. At the same time, FePO4, CrPO4 and other phosphates are poorly protected, and their large presence is not conducive to the stability of the passivation film structure, resulting in a decrease in the corrosion resistance of the material.

A study integrating in-process thermal signatures, microstructure, and corrosion behaviour of AISI 316L coatings on low carbon steel substrate deposited by laser-directed energy deposition (L-DED)

Surface coating through Laser Directed Energy Deposition (L-DED) of AISI 316L on low-carbon steel was carried out by varying laser fluence. The resulting melt pool characteristics, obtained through IR pyrometer, played a significant role in evolution of the microstructure. A higher heat input resulted in an equiaxed grain structure with finer grain sizes and improved deposition quality. The quantitative phase analysis revealed the presence of a dominant austenite phase and a secondary ferrite phase, along with traces of molybdenum carbide. Corrosion analysis reveals improved resistance at a higher laser fluence, attributed to increased content of corrosion-resistant alloying elements (Mo, Cr) and predominance of the austenite phase. Electrochemical Impedance Spectroscopy (EIS) confirms a higher corrosion resistance at a higher laser fluence, supported by a significantly higher polarization resistance and presence of a duplex-structured passive film. Results indicate that moderate laser fluence levels, ranging from 5 to 7.5 kJ/cm2, accompanied by medium to high thermal signatures and moderate cooling rates, yield coatings with refined microstructures, enhanced mechanical strength, and corrosion resistance. For superior corrosion resistance, a laser fluence of 10 kJ/cm2 is recommended, although careful consideration of its potential impact on mechanical properties is advised.

Study on S-N Curve and Fatigue Limit of Drill Pipe in Offshore Short-Radius Sidetracking Process

To evaluate the fatigue reliability of different types of drill pipes during an offshore short-radius sidetracking process, the fatigue life and limit of G105, S135, and V150 steel and a new titanium alloy drill pipe were studied in air, high-temperature conditions, drilling fluid, and drilling fluid containing H2S. First, the chemical composition, microstructure, and tensile properties of four kinds of drill pipe materials were tested. Secondly, the fitting effects of different S-N models were evaluated and identified, a fatigue test of four kinds of drill pipe under different environments (air, high temperature, drilling fluid, and H2S drilling fluid) was carried out, and the S-N curves and fatigue limits of different drill pipes under different environments were obtained. Finally, the fatigue sensitivity of drill pipes to different factors was studied, and the potential corrosion fatigue mechanism was explained. The research results show that the fatigue life of a drill pipe in a non-corrosive environment (air and high temperature) is mainly related to steel grade, and the fatigue life of a titanium alloy drill pipe is better than that of a steel drill pipe in a corrosive environment. The dense passivation film on the surface of a titanium alloy drill pipe is an important reason for its better corrosion fatigue life than that of a steel drill pipe. This study provides important data support for selecting drill pipes in offshore short-radius sidetracking.

Effect of Bias Arc on Microstructure and Corrosion Resistance of Q235/304 Dissimilar-Steel-Welded Joints.

To fully exploit the advantages of steel, the welding connection of dissimilar steels has been developed. In this work, the metallographic microstructures, elemental distributions, and electrochemical corrosion properties of the Q235 and 304 welds under different bias arcs were investigated. The arc bias caused the Q235-side heat-affected zone to widen, the microstructure consisted of ferrite and pearlite, and the ratio varied with decreasing distance from the fusion line. Elemental scans show that Cr and Ni concentration gradients exist near the fusion line. The 304-stainless-steel-side heat-affected zone was mainly composed of austenite grains, and the fusion zone was narrower but prone to cracking. Electrochemical tests revealed that 304 stainless steel had the best corrosion resistance, while Q235 had the worst corrosion resistance, and that the welded joints with an arc bias toward the 304 side had the best corrosion resistance. The samples' the passivation film which formed via electrochemical polarization had limited stability, but the over-passivation potential could be used as a reference for corrosion resistance. Overall, the arc bias and weld material properties significantly affected the microstructure and corrosion resistance of the joints.

Construction of chromium-free passivation film of pomelo peel extract on the surface of lithium-ion battery copper foil and study on anti-corrosion mechanism

Passivation treatment is the last key process to ensure the service life of copper foil for lithium-ion batteries. Although chromic anhydride commonly used in industry has an efficient passivation effect, it can threat human health and the environment. Herein, an environmentally friendly passivator is prepared from pomelo peel by a simple and economical solution extraction method, which makes copper foil have good anti-corrosion properties in air, chlorine-containing solution, and organic electrolyte. Electrochemical methods and X-ray photoelectron spectroscopy (XPS) confirm the potential of pomelo peel extractant (PP) to replace chromic anhydride as a passivating agent for copper foil. The interaction mechanism between PP and copper foil is analyzed by adsorption models, and the efficient passivation behavior of PP for copper foil is consistent with the Langmuir model. Density Functional Theory (DFT) calculations of the naringin (main component of PP) is performed to further reveal the protection mechanism of PP on copper foil. In addition, the copper foil treated by PP still has excellent electrochemical performance as lithium-ion battery current collector, indicating that the presence of PP not only protects the copper foil from corrosion, but also does not affect the conductivity of the copper foil. This research provides a new insight into the chrome-free passivation of copper foils, which is in line with the development concept of green production.

On the microstructure, corrosion behavior and surface films of the multi-principal element alloy CrNiTiV

A multi-principal element alloy consisting of equi-atomic concentrations of Cr, Ni, Ti, and V, was produced by arc melting. The CrNiTiV alloy was characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and scanning transmission electron spectroscopy (STEM), revealing a complex microstructure containing five phases. The corrosion performance of the alloy was evaluated with cyclic potentiodynamic polarization tests, indicating a low corrosion current density, a high breakdown potential and high repassivation potential. X-ray photoelectron spectroscopy and STEM were carried out after constant immersion in 0.6 M NaCl solution, revealing the passive (surface) film for each of the five phases. The Cr and V dominant phase consisted of an oxidized Cr/V-rich surface film, while the remaining four Ti-containing phases were predominantly TiO2-rich surface films. Ni enrichment and Ti deficiency were observed at the metal/oxide interface in certain Ti-containing phases.

Comparative analysis of microstructure and corrosion resistance in laser-clad austenitic and martensitic stainless-steel coatings

Post-casting austenite often possesses better corrosion resistance than martensite. In order to compare the difference of corrosion resistance between austenitic stainless steel coating (ASSC) and martensitic stainless steel coating (MSSC) in the powder metallurgical state, two stainless steel Fe-based alloy coatings of the same process parameter were prepared on the surface of 40Cr steel by using laser cladding technology. Through SEM, EBSD, XRD and electrochemical tests, the microstructure, phase and cross-section metallurgical bonding condition of the coating were studied, and the difference in corrosion resistance between the two was comprehensively analyzed. The results showed that the main phase structure of ASSC was the FCC phase, and the main phase structure of MSSC was the BCC phase. The average self-corrosion current (9.92 × 10−8 A/cm2) and average self-corrosion rate (1.04 × 10−3 g/m2·h) of MSSC were 4.77 % and 5.62 % of ASSC, respectively. In addition, the polarization resistance, impedance value, and passivation film density of MSSC are higher than ASSC, MSSC has less damage from corrosion. The combination of factors, such as fabric refinement and passivation film density, makes the corrosion resistance of MSSC better than ASSC.

Effect of passivation potential on corrosion behaviors of laser powder bed fusion FeCrCoNi high-entropy alloy

FeCoCrNi high-entropy alloy with uniform chemical composition was obtained by laser powder bed fusion. The potentiodynamic polarization tests showed that passive current increased with selected higher passivated potential in borate buffer solution. The semiconductor characteristic measurement displayed that passive films on laser powder bed fusion sample exhibited bilayer characteristics in the corrosion environment. Higher passivation potential facilitated to induce more point defects in the passive films, which resulted into incompact surface passive films on laser powder bed fusion sample. Therefore, the resistance to corrosion for the FeCoCrNi high-entropy alloy obtained by new technology decreased with higher passivation potential.

A Study of the Corrosion Resistance of 316L Stainless Steel Manufactured by Powder Bed Laser Additive Manufacturing

Commercially available 316L (1.4404) stainless steel is commonly used for industrial filtration due to its combination of good material properties, particularly its corrosion resistance, which is a critical factor for filters in corrosive (e.g., saltwater) environments. Recently, laser powder bed fusion (LPBF) has enabled new more complex and efficient filtration pieces to be manufactured from this material. However, it is critical to know how the corrosion resistance is affected by this manufacturing strategy. Here, the corrosion resistance of LPBF manufactured 316L stainless steel is compared with wrought 316L sheet. The corrosion of the samples in saltwater was assessed with asymmetric electrochemical noise, potentiodynamic polarisation curve, and electrochemical impedance spectroscopy. The samples before and after corrosion were examined with scanning electron microscopy and energy-dispersive spectroscopy. The LPBF samples had higher corrosion resistance than the sheet samples and were more noble. The corrosion resistance of the LPBF sample increased with time, while the wrought sample corrosion resistance reduced over time. The corrosion mechanism of both samples was stable with time, formed of a passive film process and a bared material process. This paper presents the first study about the temporal evolution of the LPBF 316L stainless steel corrosion mechanism.

Discharge Properties and Electrochemical Behaviors of Mg-Zn-xSr Magnesium Anodes for Mg-Air Batteries.

In this work, the electrochemical and discharge properties of Mg-Zn-xSr (x = 0, 0.2, 0.5, 1, 2, and 4 wt.%) alloys used as anodes for Mg-air batteries were systematically studied via microstructure characterization, electrochemical techniques, and Mg-air battery test methods. The addition of Sr refines the grain size, changes the composition and morphology of the passivation film and discharge products, and enhances the electrochemical properties of the alloy. Excessive Sr addition breaks the grain boundaries and precipitates a large number of Sr-rich phases, resulting in microgalvanic corrosion and the 'chunk effect'. The anode efficiency of Mg-Zn-1Sr is the highest at a current density of 10 mA cm-2, reaching 61.86%, and the energy density is 2019 mW h g-1. Therefore, Sr is a microalloying element that can optimize the electrochemical performance of Mg-air battery alloy anodes.

Corrosion resistance and passive film stability of laser direct energy deposited TiVZrNbAl lightweight multi-principal element alloy

This work reports the corrosion behaviour of a novel laser direct energy deposited Ti45V30Zr12Nb12Al1 lightweight multi-principal element alloy (MPEA) in a 0.6 M NaCl solution. The MPEA exhibits superior corrosion resistance to typical titanium alloys, including Ti80. Its excellent corrosion resistance is attributed to a passive film with bipolar semiconducting behaviour and an amorphous structure. This unique feature inhibits anion permeation from the electrolyte and cation dissolution from the passive film. Further analyses revealed that Nb alloying effectively reduces the point defect density in the passive film, enhancing its ability to resist attacks by chloride ions.

Enhanced performance of ambient-air processed CsPbBr3 perovskite light-emitting electrochemical cells via synergistic incorporation of dual additives

Metal halide perovskite light-emitting electrochemical cells (MHP-LECs) are promising due to their facile solution processability and exceptional optoelectrical properties. However, commercialization is hindered by poor thin-film coverage and the need for glovebox processing. This study addresses these issues by incorporating poly(ethylene oxide) (PEO) and potassium hexafluorophosphate (KPF6) into cesium lead bromide perovskite (CsPbBr3) emitting layers (EML), processed under ambient-air conditions. These perovskite composite thin films were spin-coated on a preheated substrate, and the device structure was ITO/PEDOT:PSS/EML/Al. Notably, the MHP-LEC based on CsPbBr3:PEO:KPF6 (100:65:0.2, weight ratio) exhibited pure-green emission with a peak at 524 nm and a narrow full width at half-maximum of 27 nm. Compared to a reference device (CsPbBr3:PEO (100:65, weight ratio)), the new device showed 1.5-, 4-, and 5-fold improvements in current density, electroluminescence (EL) intensity, and lifetime, respectively. These enhancements are attributed to reduced non-radiative current leakage, improved film surface coverage and passivation, and balanced charge carrier injection and transportation. This study offers a straightforward approach for processing CsPbBr3 thin films under ambient-air conditions, enhancing the EL performance of MHP-LECs.

Protective Effects of Small Molecular Inhibitors on Steel Corrosion: The Generation of a Multi-Electric Layer on Passivation Films

The durability of reinforced concrete structures is significantly influenced by the effectiveness of small molecular inhibitors in preventing the corrosion of steel reinforcements. In a concrete environment, the passive film on steel bars serves as a critical protective component. In this study, a molecular dynamics (MD) simulation is used to study the inhibition mechanism of chloride ions by common corrosion inhibitors (2-Amino-2-thiazoline) in concrete in an excess chloride solution. The results reveal that inhibitors adsorb onto the steel surface primarily through van der Waals forces, with more than 90% of the adsorption occurring vertically. Despite this strong adsorption, inhibitors alone do not form a protective film. In the presence of chloride ions, which frequently penetrate concrete, the coverage rate of inhibitors on the steel surface decreases from 74% to 64%. Nevertheless, inhibitor molecules still provide substantial protection in chloride-rich concrete environments. Further analysis indicates that inhibitor molecules inhibit chloride ions in two ways. Corrosion inhibitor molecules actively desorb from the steel surface to capture chloride ions and prevent them from approaching. Additionally, inhibitors form a multi-electron layer on the steel surface to enhance passive film protection and hinder chloride ion diffusion through Coulombic interactions.

A bi-functional self-healing epoxy composite coating based on coordinated functionalized attapulgite/graphene oxide

Applications for graphene oxide (GO) in the field of corrosion protection will be severely constrained by the material’s poor dispersion and compatibility with epoxy resins, as well as the absence of self-healing corrosion protection in GO-based epoxy coatings. In this work, we developed a bi-functional 2-mercaptobenzothiazole (MBT) inhibitor-encapsulating GO-based nanocomposite (GAM) with pH-responsive release by implanting attapulgite (ATP) nanorods on the surface of GO. Additionally, GO-based nanocomposite can form covalent connections with epoxy resins and be evenly distributed in epoxy film via a ring opening process. Moreover, improved epoxy film compatibility and dispersion result in elevated mechanical strength and better impermeability, which prevent corrosion in both the active and passive modes. The corrosion resistance of GAM self-healing coating increased as the submersion period exceeded 24 h up to 0.54 M Ω cm2, resulting in the release of MBT inhibitor to form a passivation film at the defective region. Moreover, the improved charge transfer resistance (Rct) and the coating’s resistance to corrosive species (Rc) attribute to the self-healing ability of the GAM coating. The incorporation of GAM (2 %) nanocomposites into epoxy films enables long-term protection of AA2024-T3 by combining passive and self-healing corrosion prevention.

Bio-corrosion behaviors and bio-compatibilities of TiNbZrTa and TiNbZrTaMo high entropy alloys

The bio-corrosion behavior and bio-compatibility of TiNbZrTa and TiNbZrTaMo high entropy alloys (HEAs) are crucial for their efficient maintenance during biological implantation. In this work, TiNbZrTa and TiNbZrTaMo HEAs were successfully prepared via vacuum melting, with a β-type titanium alloy Ti35Nb7Zr5Ta, exhibiting good biocompatibility used as a comparison. Due to the high entropy effect of equal atomic ratios, both TiNbZrTa and TiNbZrTaMo HEAs exhibit body-centered cubic (BCC) structure and lattice distortion compared to the β titanium alloy Ti35Nb7Zr5Ta. Mo elements contribute to the formation of a new BCC phase, resulting in a white matrix rich in Ta and Mo, and a dark second phase rich in Ti, Zr, and Nb. Electrochemical test results at 37 °C shown that TiNbZrTa has a wider and more stable passivation area than TiNbZrTaMo. The XPS results shown that formation of the passive film is related to the main elements added. Ti, Nb, Ta and Mo formed oxides via the solid-liquid interface and migrate inward, while Zr is formed at the passivation film/metal substrate interface and migrates outward, finally forming the layered structure of the passivation film. Additionally, the cytotoxicity test of mouse fiber cells was carried out to evaluate the biocompatibility of the HEAs. The results shown that the cell proliferation rate of TiNbZrTa and TiNbZrTaMo HEAs reached 0 and 1, respectively, with TiNbZrTa exhibiting better biocompatibility, as adding Mo reduced the cell proliferation rate. These findings may provide a method for predicting the bio-corrosion behavior and bio-compatibility of HEAs used for biological implantation.

Effect of Cr on the microstructure and corrosion behavior of nickel-based alloys in hydrochloric acid

Nickel-base alloy is a type of metal material with excellent properties and is widely used in many fields. However, in the harsh environment of the acid solution, corrosion causes the reduction of the service life of the alloys, thereby limiting the alloys' use and development. In this paper, the effect of Chromium (Cr) content on the microstructure and corrosion behavior of nickel-based alloys in hydrochloric acid (HCl) was studied by scanning electron microscopy (SEM), energy dispersive spectrum (EDS), electron backscatter diffraction (EBSD) and electrochemical workstation. Meanwhile, X-ray photoelectron spectroscopy (XPS) was used to investigate the composition and properties of the surface passive films. For the Cr20 and Cr30 alloys with a single face-centered cubic (FCC) structure, the Cr2O3 content in the passive films increased with the Cr content, effectively improving the corrosion resistance. As the Cr content continued to increase, the second phases having a body-centered cubic (BCC) lattice were precipitated both in the Cr40 and Cr50 samples, inducing microgalvanic corrosion, thus deteriorating the corrosion resistance. XPS results showed that, in the Cr30 alloy, the relative content of Cr2O3 and the bound water were the highest, indicating that its passive film had the best corrosion resistance. For the passive film, the pitting resistance was related to Cr content, appropriate Cr content improved the corrosion resistance.

Assemble of porous heterostructure thin film through CuS passivation for efficient electron transport in dye-sensitized solar cells

Three different modified solar cells have been passivated with copper sulfide (CuS) on a TiO2 electrode and manganese sulfide (γ‐MnS) hexagonal as photon absorbers. The MnS were prepared using (a-c) bis(N‐Piperl‐N‐p‐anisildithiocarbamato)Manganese(II) Complexes Mn[N-Piper‐N‐p‐Anisdtc] as (MnS_1), N‐p-anisidinyldithiocarbamato Mn[N‐p-anisdtc] as (MnS_2) and N‐piperidinyldithiocarbamato Mn[N‐piperdtc] as (MnS_3). The corresponding passivated films were denoted as CM-1, CM-2, and CM-3. The influence of passivation on the structural, optical, morphological, and photochemical properties of the prepared devices has been investigated. Raman spectra show that the combination of this heterostructure is triggered by the variation in particle size and surface effect, thus resulting in good electronic conductivity. The narrow band gaps could be attributed to good interaction between the passivative materials on the TiO2 surface. CM-2 cells, stability studies show that the cell is polarized and current flows due to electron migration across the electrolyte and interfaces at this steady state. The cyclic voltammetry (CV) curve for the CM-3 with the highest current density promotes the electrocatalytic activity of the assembled solar cell. The catalytic reactions are further confirmed by the interfacial electron lifetimes in the Bode plots and the impedance spectra. The current–voltage (J–V) analysis suggests that the electrons in the conduction band of TiO2/CuS recombine with the semiconductor quantum dots (QDs) and the iodolyte HI-30 electrolyte, resulting in 5.20–6.85% photo-conversions.

THE EFFECT OF A Cr-FREE FINGERPRINT-RESISTANT PASSIVATION FILM ON THE PERFORMANCE OF HOT-DIP 55 % Al-Zn COATED STEEL

Cr-free fingerprint-resistant hot-dip 55 w/% Al-Zn coated steel (CFAZCS) is a upmarket steel plate product that is widely used in consumer goods with high added value, such as LCD back panels for monitors, as well as various electrical and electronic products. Passivation is a crucial process in the production of CFAZCS, greatly affecting the overall performance of the CFAZCS product. A comprehensive evaluation of passivation films from different manufacturers on the performance of CFAZCS can assist production enterprises in optimizing and controlling the product quality according to the requirements of target customers. This article comprehensively tests and evaluates the performance of corrosion resistance, acid/alkali resistance, anti-yellowing/blackening, paint adhesion, abrasion resistance, fingerprint resistance, and the conductivity of mainstream, commercially available, Cr-free, fingerprint-resistant, passivation solutions, providing guidance for the selection of passivation solutions in production processes.