Passive Film Research Articles

Effect of annealing on microstructure and corrosion resistance of W+in-situ TiC enhanced CoCrFeNiSi0.2 high entropy alloy coatings by laser cladding

The W+in-situ TiC reinforced CoCrFeNiSi0.2 high-entropy alloy coating (The alloy coating) was prepared using laser cladding, and the effect of different annealing temperatures on the microstructure and corrosion resistance of the alloy coating was studied. The results indicated that annealing induces changes in the proportion of FCC and BCC phases in the coating matrix as well as the shape of carbides in the coating. Potentiodynamic polarization and electrochemical impedance experiments in 3.5 wt% NaCl solution revealed that the coating annealed at 1100°C exhibits the best corrosion resistance due to the presence of a single FCC phase and the formation of spherical carbides. Surface morphologies after corrosion showed deeper pits on the coating annealed at 700°C, which exhibited the poorest corrosion resistance due to the combined effects of galvanic and occluded cell corrosion. Potentiodynamic polarization curves demonstrated the presence of passive films on the surfaces of all four samples, and surface scan results after corrosion suggest that the passive film on the coating surface mainly consists of Ti- and W-containing oxides.

Enhanced Anticorrosion, Antifouling, and Tribological Properties of PANI Composite Coating Reinforced by PVA, 2-Aminophenol, and Acrylic to Fabricate Sustainable Passive Film on 304 SS

Enhanced Anticorrosion, Antifouling, and Tribological Properties of PANI Composite Coating Reinforced by PVA, 2-Aminophenol, and Acrylic to Fabricate Sustainable Passive Film on 304 SS

Preparation of high-performance electroplated zinc coatings using modified DESs method

This study suggests a new process for zinc recycling in the iron and steel industry, that is, using RHF zinc-containing refined dust as the raw material and ChCl-urea DES (Reline) as the medium. The solid waste from the bottom-turning furnace is leached out, and the resulting zinc is plated directly onto automobile plates. This paper focuses on the utilization of EDTA as an additive to improve the overall performance of the zinc coatings. The results demonstrated that the addition of EDTA realized the modulation of the morphology of the coatings, which made the surface milky white and uniformly bright. The coating consists of hexagonal lamellar grains, dominated by (002) crystalline surfaces that grow at small angles, and the surface flatness is dramatically improved. Most importantly, the hardness of the modified coatings was increased by 70.0% and the coefficient of friction was reduced by about 29.2% compared with the coatings obtained in the pure solution. The addition of EDTA led to the formation of a surface passivation film during the corrosion process, which significantly improved the corrosion resistance of the material surface and the corrosion rate was reduced by 0.355 mm.A−1.

Challenges and Progress in Rechargeable Magnesium‐Ion Batteries: Materials, Interfaces, and Devices

AbstractRechargeable magnesium‐ion batteries (RMBs) have garnered increasing research interest in the field of post‐lithium‐ion battery technologies owing to their potential for high energy density, enhanced safety, cost‐effectiveness, and material resourcefulness. Despite substantial advancements in RMB research, a number of intrinsic challenges remain unresolved, such as the strong Coulombic interaction between Mg2+ and the host crystal structure of cathode materials, sluggish Mg2+ diffusion kinetic, poor electrolyte compatibility, and the formation of passivation films on the Mg anode interface. These issues hinder the commercial applications of RMBs. This review provides a comprehensive overview of the progress in key areas of RMB research, including representative magnesium‐ion storage cathode/anode materials and magnesium‐ion conducting electrolytes. Additionally, recent developments in electrode‐electrolyte interface regulations and pouch‐cell fabrication are outlined, highlighting current challenges and the implementation of effective solutions. Finally, future research directions are proposed to guide the development of high‐performance RMBs with practical applications.

Role of Te-RE alloying on the passive film and pitting corrosion behavior of 316L stainless steel

This work reports the mechanism of corrosion resistance enhancement of 316 L stainless steel after Te-RE alloying. The individual MnS inclusions are replaced by composite inclusions, resulting in a reduced risk of pitting corrosion. The decrease of inclusion amount and Volta potential difference between inclusion and matrix induced by the addition of Te/La promoted the stability of the inclusions and lessened the active sites for pitting corrosion. TeO2 formed in the passive film with Te treatment could be easily reduced by Cr and Mo, and resulting in a significant increasing of MoO2 and Cr2O3 content in the passive film. This enhanced the stability of the passive film. Te and RE exhibited a synergistic effect on the increase of Cr and Mo in the passive film, resulting in a further improvement of the passive film. However, RE could not exist in the passive film stably due to its poor thermodynamic stability of the rare earth oxides, and only acted as a bridge for the formation of Cr and Mo oxides.

Microstructures and corrosion behaviors under sodium chloride aqueous conditions of Co-free non-equiatomic Al0.32CrFeTi0.73(Ni1.50-xMox) (x=0, 0.23) high entropy alloys

High entropy alloys (HEAs) were prepared using a vacuum arc melting method. The effect of Mo partially substituting Ni on the crystal structure and corrosion behaviors was studied. The results show that the HEAs exhibited a multiphase complex crystal structure which was composed of a BCC matrix and several intermetallic phases. The HEAs showed good corrosion resistance despite multiphase heterogeneity. But cyclic polarization showed that the HEAs were susceptible to pitting corrosion. Selective corrosion of Cr-depleted phases after polarization tests was attributed to the galvanic corrosion between Cr-depleted and Cr-rich phases. The spontaneous passive films on the HEAs surface were characterized by p-type semiconductor. Existence of Mo element of the HEAs accelerated passivation reaction kinetics, improved the stability of passive film, accordingly, acquired better general and pitting corrosion resistance.

Investigations of Crucial Factors for the Non-Covalent Functionalization of Black Phosphorus (BP) using Perylene Diimide Derivatives for the Passivation of BP Nanosheets.

The non-covalent functionalization of black phosphorus (BP) was studied with a scope of ten tailor-made perylene diimides (PDIs). A combination of UV/Vis-, fluorescence-, as well as Raman spectroscopy and atomic force microscopy was used to investigate the structural factors, which contribute to a pronounced PDI-BP interaction and thus support the protection of BP nanosheets against oxidative degradation. We were able to show, that water-soluble, amphiphilic PDIs with highly charged head groups can be used for the non-covalent functionalization of BP in aqueous media. Here, based on the hydrophobic effect, an efficient adsorption of the respective PDI molecules takes place and leads to the formation of a passivating film, yielding a considerable stabilization of the BP flakes under ambient conditions exceeding 30 days.

Effect of heat treatment on microstructure, mechanical properties and corrosion resistance of 7075 aluminum alloys fabricated by improved friction stir additive manufacturing

The use of an improved stirrng pin broadened the effective bonding area in the friction stir additive manufacturing (FSAM) of 7075 aluminum alloy. A systematic investigation was conducted to examine the effects of different heat treatment (T6, T73, and RRA) processes on the microstructure, tensile strength and corrosion resistance of as-fabricated (AS) specimen. The findings revealed that different heat treatments had minimal impact on the grain size, texture strength, and dislocation density. Variations in strength and corrosion resistance were primarily attributed to the size and distribution of precipitates. Following T6 heat treatment, the intragranular precipitates (IGPs) were smaller, with a higher proportion of η', while the grain boundary precipitates (GBPs) were coarser η, continuously distributed along grain boundaries. Consequently, T6 specimen showed the highest tensile strength, reaching 568 MPa, but had lower corrosion resistance than AS specimen due to precipitate-induced disruption of the passive film. The T73 heat treatment resulted in significant coarsening of IGPs, with a substantial transformation of η' to η, thereby reducing the precipitation strengthening effect. The coarsening of GBPs led to their discontinuous distribution along grain boundaries, which significantly increased the corrosion resistance. After RRA heat treatment, IGPs consisted of numerous fine η', while the coarser GBPs sporadically dispersed along grain boundaries. The strength of RRA specimen was only about 6 % lower than that of T6 specimen, but its corrosion resistance was significantly improved.

The effect of Nb additions on the passive behavior of NiTi shape memory alloys

This study explores the passivity and localized corrosion behavior of Ni(100-x)/2Ti(100-x)/2Nbx shape memory alloys (where x = 3, 6, and 9 at.%) through potentiodynamic and potentiostatic polarization tests in 3.5 wt% NaCl solution. The results reveal a significant dependence of the surface passive film’s stability on the Nb concentration. Using X-ray photoelectron spectroscopy (XPS), the chemical composition of the passive films formed on the NiTiNb alloys was characterized. Microstructural analysis showed that increasing Nb content affects the volume fraction of the eutectic microconstituent, leading to the suppression of martensite and secondary Ni-Ti phases in the microstructure with higher Nb additions. The findings demonstrate that localized corrosion resistance improves with Nb additions, attributed to the incorporation of Nb2O5 into the TiO2 passive film, enhancing its protective capacity. Remarkably, the NiTi shape memory alloy exhibits immunity to localized corrosion when 9 at.% Nb is added.

Influence of grain sizes and secondary phases on the mechanical behavior and corrosion resistance in a non-equiatomic NiCrCoFeMoAlTi high-entropy alloy

Single-phase face-center cubic (FCC) structured Ni27.7Cr24Co23.5Fe15.7Mo1.6Al3Ti4.5 high-entropy alloy (HEA) samples with different grain sizes were first achieved, suggesting smaller grain size improved corrosion resistance and strength. Subsequently, aging was performed on the sample with the smallest grain size (∼9.5 μm), leading to the formation of lots of nano-sized spherical coherent L12 precipitates at FCC grain interior, along with some σ phase and non-spherical L12 precipitates at grain boundaries. Therefore, a superior combination of mechanical and corrosion properties was achieved. Secondary phases caused chemical and structural changes in the passive film due to galvanized corrosion, leading to slightly lower corrosion resistance.

Passive isothermal film with self-switchable radiative cooling-driven water sorption layer for arid climate applications

Reducing substantial energy demand of active heating, ventilation, and air conditioning in arid climates is of paramount importance. Here, we develop a millimeter-scale passive isothermal film that maintains temperature near 25 °C without relying on energy consumption solely through natural phenomena. A radiative cooling unit comprising polydimethylsiloxane (PDMS) with diffraction grating and fused SiO2/Ti/Ag film facilitates radiative cooling during daylight hours. Net thermal energy is stored through water desorption of porous materials (latent cooling) and dissolution of ammonium nitrate in water (endothermic reaction). At nighttime, thermal emission is suppressed by the destructive interference of PDMS diffraction, and thermochemical reverse reaction occurs to sustain temperature in response to heat loss from the ambient environment. It reduces cooling and heating loads by approximately −1.1 and 0.3 kW m−2, respectively, throughout a full day. Our results indicate the potential of designing a passive system suitable for human habitation without an active system.

Corrosion inhibitors in H2O2 system slurry for Ru based barrier layer Cu interconnect chemical mechanical polishing and optimization

Ruthenium (Ru) has the advantages of low resistivity, high thermal stability, and good adhesion and wettability, making it an important solution for breaking through the 14 nm process as a new barrier layer material for multilayer copper interconnect. The purpose of copper (Cu) interconnect Ru-based barrier layer chemical mechanical polishing (CMP) is to obtain a highly flat surface, which not only includes the ideal Ru removal rate and selectivity of the Cu/Ru removal rate, but also inhibition of Cu corrosion. In this article, the corrosion inhibition mechanism of environmentally friendly and highly water-soluble inhibitor 5-methylthio-1 H-tetrazole (MTT) on Cu was studied. The inhibitory effect of MTT on Cu was analyzed through static etching rate testing, electrochemical experiments, and surface characterization. A systematic test was conducted on the planarization performance of the optimized polishing slurry. The corrosion inhibition mechanism of MTT on Cu was revealed through quantum chemical calculations and XPS testing. The experimental results show that the corrosion inhibitor MTT can effectively improve the surface quality of Cu. Quantum chemical calculations and experimental results indicate that MTT can be adsorbed on the surface of Cu through both physical and chemical methods, forming a dense passivation film, thereby inhibiting the corrosion of Cu. The optimized ratio of Ru-based barrier layer CMP polishing slurry was 5 wt% SiO2, 0.15 wt% H2O2, 20 mM ethylenediamine (EDA), 5 mM K4Fe(CN)6, and 2000 ppm MTT, resulted in the Cu/Ru removal rate selectivity of 1:1.18 and the Cu/Ru corrosion potential difference of 3 mV. The average correction values for dishing and erosion on the test pattern wafer of the Ru barrier layer were 355 Å and 280 Å, respectively. The results of this study indicate that MTT is an effective copper corrosion inhibitor in alkaline H2O2-based polishing slurry, providing meaningful references for Ru-based barrier layer copper interconnect CMP.

Study of endogenous chloride ion content on the behavior of steel bar depassivation in sea sand concrete

In this study, we investigated the chloride concentration in sea sand that induces corrosion in steel bars, as well as the corrosion mechanisms of steel bar within sea sand concrete. Different analytical techniques indicated that the chloride concentration for steel bar corrosion in sea sand concrete was 0.03 % (when the water-binder ratio was in the range of 0.4–0.6). First, the calcium silicate in sea sand concrete reacted with Fe3+ to reduce the compactness of the oxide layer and increase the corrosion risk of steel bars. Second, as the water-binder ratio and chloride concentration gradually increased, the loose structure of the passive film increased, and the relatively dense structure decreased, which made it easier for chloride ions to penetrate the outer layer of the passive film to erode the steel matrix. Besides, the reaction of chloride ions with C3A to form Friedel's salt optimized the pore structure and reduced the content of free chloride ions. However, the adverse effect of chloride ions on the passive film of steel bars exceeded the beneficial impact of porosity reduction. These findings allow us to better apply sea sand to improve the sustainable development of environment.

Linear dependence of potential drop at the passive film/solution interface on film-formation potential and pH: Combining first-principles calculations with experiments

Potential drop at the oxide film/solution interface plays a critical part in numerous electrochemical processes, especially for the passivated metal-electrolyte system, affecting the passive film breakdown and the pitting initiation. There are still some controversies over the dependence of potential drop at the passive film/solution interface (φf/s) on potential and pH of electrolyte. Herein, we develop a model presenting the linear dependence of φf/s on both potential and pH, as represented by φf/s=φf/s(V=0,pH=0)0+αV+βpH. By analyzing the surface charge (i.e., point of zero charge, pHpzc) and performing first-principles calculations, we provide the insights into the effect of potential and pH on the φf/s, and into the linear relation between φf/s with pH beyond the Nernst relation that is attributed to the role of point defects in pHpzc of passive film on iron. In addition, two methods, e.g., a combination of Mott-Schottky measurement with first-principles, contact angle titration, are suggested to determine the values of α, β and φf/s(V=0,pH=0)0, respectively. The study of passivity of iron in borate buffer solutions validates our model.

Electrochemical stability of biodegradable Zn-Cu alloys through machine-learning accelerated high-throughput discovery.

Zn-Cu alloys have attracted great attention as biodegradable alloys owing to their excellent mechanical properties and biocompatibility, with corrosion characteristics being crucial for their suitability for biomedical applications. However, the unresolved identification of intermetallic compounds in Zn-Cu alloys affecting corrosion and the complexity of the application environment hamper the understanding of their electrochemical behavior. Utilizing high-throughput first-principles calculations and machine-learning accelerated evolutionary algorithms for screening the most stable compounds in Zn-Cu systems, a dataset encompassing the formation energy of 2033 compounds is generated. It reveals that most of the experimentally reported Zn-Cu compounds can be replicated, especially the structure of R32 CuZn5 is first discovered which possesses the lowest formation energy of -0.050 eV per atom. Furthermore, the simulated X-ray diffraction pattern matches perfectly with the experimental ones. By formulating 342 potential electrochemical reactions based on the binary compounds, the Pourbaix diagrams for Zn-Cu alloys are constructed to clarify the fundamental competition between different phases and ions. The calculated equilibrium potential of CuZn5 is higher than that of Zn through the forward reaction Zn + CuZn5 ⇌ CuZn5 + Zn2+ + 2e-, resulting in microcell formation owing to the stronger charge density localization in Zn compared to CuZn5. The presence of chlorine accelerates the corrosion of Zn through the reaction Zn + CuZn5 + 6Cl- + 6H2O ⇌ Cu + 6ZnOHCl + 6H+ + 12e-, where the formation of ZnOHCl disrupts the ZnO passive film and expands the corrosion pH range from 9.2 to 8.8. Our findings reveal an accurate quantitative corrosion mechanism for Zn-Cu alloys, providing an effective pathway to investigate the corrosion resistance of biodegradable alloys.

Effect of intermittent non-isothermal aging on the microstructure and properties of Al–Zn–Mg–Cu alloy

The proposition of an intermittent non-isothermal aging (IM-NIA) is an innovative approach to address the challenge of balancing the mechanical properties and corrosion resistance of Al–Zn–Mg–Cu alloys. The effects of IM-NIA on the hardness, corrosion resistance and microstructure morphology of Al–Zn–Mg–Cu alloys were investigated by hardness test, intergranular corrosion test (IGC), exfoliation corrosion test (EXCO), electrochemical corrosion test and combined with transmission electron microscopy (TEM) observation. The results showed that the hardness of the alloy was the highest at 186HV after intermittent post-tempering to 180 °C (IM-H180). The intergranular corrosion depth is the smallest, the corrosion rate is the slowest, and the exfoliation corrosion rating is EA. In addition, the alloy matrix precipitated phase has the smallest average diameter, the highest volume fraction, the strongest ability to repair the passivation film, and the strongest resistance to Cl− erosion; At the same time, the grain boundary precipitation phase is intermittent and multilinear parallel distribution, PFZ is the widest, hindering the anodic corrosion channel, slow corrosion progress and improve corrosion resistance.

Improving Perovskite Solar Cell Performance and Stability via Thermal Imprinting-Assisted Ion Exchange Passivation.

The latest development in perovskite solar cell (PSC) technology has been significantly influenced by advanced techniques aimed at passivating surface defects. This work presents a new approach called thermal imprinting-assisted ion exchange passivation (TIAIEP), which delivers a different approach to conventional solution-based methods. TIAIEP focuses on addressing surface imperfections in solid-state films by using a passivator that promotes ion exchange specifically at the defect sites within the perovskite layer. By adjusting the time and temperature of the TIAIEP process, we achieve substantial enhancement in the creation of a compositional gradient within the films. This optimization slows the cooling rate of hot carriers, leading to minimizing charge recombination and improving the device performance. Remarkably, devices treated with TIAIEP achieve a 22.29% power conversion efficiency and show outstanding stability, with unencapsulated PSCs maintaining 91% of their original efficiency after over 2000 h of storage and 90% efficiency after 1200 h of constant illumination. These results highlight TIAIEP's effectiveness in mitigating surface defects, improving both the photoelectric and stability performance of PSCs, and indicating significant potential for large-scale application in perovskite film passivation, promoting the widespread adoption of this technology.

Laser clad CoCrFeNiTixNby hypoeutectic high-entropy alloy coating: Effects of Ti and Nb content on mechanical, wear and corrosion properties

High-entropy alloys (HEAs) exhibit significant potential for advanced wear and corrosion-resistant applications. This study investigates the influence of Ti and Nb doping on the microstructure, phase composition, and properties of CoCrFeNiTixNby HEAs synthesized using high-speed laser cladding (HLC). The results demonstrate that increasing Ti and Nb content transforms the coating structure from a face-centered cubic (FCC) phase to a hybrid structure comprising FCC, body-centered cubic (BCC), and Laves phases, leading to a linear enhancement in surface hardness. The incorporation of Ti and Nb not only promotes the preferred orientation of the FCC phase (111) crystal plane but also significantly enhances tensile strength, though this comes at the expense of reduced plasticity. Specifically, the CoCrFeNiTi0.6Nb0.15 coating attains an ideal balance between strength and ductility, with a tensile strength of 1641.8 MPa and a tensile strain of 15.9 %, achieved through the formation of a eutectic structure. This coating also exhibits superior wear resistance and outstanding corrosion resistance, which are attributed to the stability of the passivation film, reinforced by the (111) crystal plane and high-density dislocations. These findings provide both theoretical and empirical foundations for the design of high-performance HEAs, underscoring their potential in industrial applications requiring robust wear and corrosion resistance.

Mechanism of Improving Etching Selectivity for E-Beam Resist AR-N 7520 in the Formation of Photonic Silicon Structures

The selectivity of the reactive ion etching of silicon using a negative electron resist AR-N 7520 mask was investigated. The selectivity dependencies on the fraction of SF6 in the feeding gas and bias voltage were obtained. To understand the kinetics of passivation film formation and etching, the type and concentration of neutral particles were evaluated and identified using plasma optical emission spectroscopy. Electron temperature and electron density were measured by the Langmuir probe method to interpret the optical emission spectroscopy data. A high etching selectivity of 8.0 ± 1.8 was obtained for the etching process. The optimum electron beam exposure dose for defining the mask was 8200 pC/m at 30 keV.

The effect of coordinated deformation on the microstructure and corrosion performance of 316L stainless steel/20# carbon steel composite pipes during hot compression

Through hot compression experiments under different deformation conditions (0.1 s−1 at 900 °C/1050 °C/1200 °C), the effect of coordinated deformation on microstructure evolution was studied, and the influence of different initial microstructures on corrosion performance was subsequently investigated. As a result, strain preferentially concentrated in 20#, resulting in dynamic recrystallization (DRX). Subsequently, grain refinement and DRX occurred in 316L. Additionally, the farther from the interface, the weaker the coordinated deformation effect. Compared to only 316L, the 316L in composite pipes has higher density of dislocations and low-angle grain boundaries. Corrosion resistance is related to the microstructure after coordinated deformation, decreasing with the increase in dislocation density, low-angle grain boundaries, and recrystallized grain size. At 1200 °C, the effect of coordinated deformation on 316L is significantly reduced. The passivation film resistance is 2.14 × 106 Ω·cm2, similar to that of only 316L. Therefore, appropriately increasing the hot rolling temperature and the thickness of 316L in the billet can reduce the effect of coordinated deformation on the DRX of 316L, thereby maintaining the pitting corrosion resistance of 316L.