Passivation of Al–Cr–Fe and Al–Cu–Fe–Cr complex metallic alloys in 1 M H2SO4 and 1 M NaOH solutions

The corrosion mechanisms of Al–Cr–Fe and Al–Cu–Fe–Cr complex metallic alloys have been investigated by potentiodynamic and potentiostatic polarization. Very good passivation of the Al–Cr–Fe surface is exhibited from 1 M H₂SO₄ to 1 M NaOH solutions, which was confirmed by ICP-OES analysis over a period of 273 days. Potentiostatically formed passive films analysed by XPS revealed chromium enrichment in the outermost layer of the aluminium oxy-hydroxide film. Although Al–Cu–Fe–Cr showed passivation during potentiodynamic polarization, heavy active corrosion at OCP was revealed by ICP-OES. For the Al–Cu–Fe–Cr alloy, the 10% content of Cr is insufficient to maintain a protective “chemically stable” Cr oxide/hydroxide.     

Electrochemical corrosion kinetics of spark plasma sintered Nd–Fe–B permanent magnets in NaCl electrolyte

Abstract

Static state immersion experiments, polarisation curve and electrochemical impedance spectroscopy tests have been applied to investigate the corrosion kinetics for both spark plasma sintered (SPS) and conventional sintered Nd–Fe–B magnets in NaCl electrolyte. Effect of microstructure modification on their chemical stability of the magnets was discussed. The electrochemical reactions of both magnets are controlled by the step of active substances adsorption process at the open circuit potential and the anodic potential, which turn to diffusion process at the cathodal potential. Although both magnets are susceptible to corrosion in saline electrolytes, SPS magnets are more corrosion resistant than conventional sintered magnets due to their special microstructure that is different from those of conventional sintered magnets. In SPS magnets, the grain size of the Nd₂Fe₁₄B main phase is fine and uniform, only a few Nd rich phase form along the grain boundaries of Nd₂Fe₁₄B phase, while most of them agglomerate into triple junctions as small particles. Such microstructure effectively restrains the aggressive intergranular corrosion along Nd rich phases. As a result, the SPS magnet possesses excellent corrosion resistance in NaCl electrolyte.     

Corrosion behaviour of cermet-based coatings with a bond coat in 0.5 M H2SO4

The corrosion behaviour of an HVOF Ni–5Al/WC–17Co coating on Al-7075 is investigated in 0.5 M H₂SO₄. In the temperature range of 25–45 °C, the coating exhibits pseudopassivity that effectively protects from localized corrosion. At 25 °C, pseudopassivity proceeds via three stages: during the first stage, oxidation of W in the binder phase occurs. The second stage is characterized by oxidation of W in both the binder and the carbide particles. The third stage is characterized by intensive hydration of WO₃ and formation of Co₃O₄. During the second and third pseudopassive stages, the formation of a bi-layer surface film is postulated. The inner layer, consisting of anhydrous oxides, has a barrier character. The outer layer, composed of WO₃ · xH₂O, is unstable. In case of surface film disruption, the bond coat successfully hinders corrosion propagation into the Al-alloy. Higher electrolyte temperatures lead to faster corrosion kinetics and higher tendency for pitting.     

Hot corrosion of a novel (Ni,Co)O/(Ni,Co)Fe2O4 composite coating thermally converted from an electrodeposited Ni–Co–Fe2O3 composite coating

Ni–Co–Fe₂O₃ composite coatings were successfully developed by sediment co-deposition. In order to improve their hot corrosion resistance, a pre-oxidation treatment was conducted at 1000 °C for 6 h. The corrosion behaviour of the oxidised composite coating was investigated at 960 °C in an atmosphere consisting of a mixture of Na₃AlF₆–AlF₃–CaF molten salts and air. They exhibited good hot corrosion resistance due to not only the pre-formed oxide scale with (Ni,Co)O and (Ni,Co)Fe₂O₄ phases after pre-oxidation, but also the formation of (Ni,Co,Fe)Al₂O₄ phases in the outer layer and a well-distributed NiFe₂O₄-enriched phase along the grain boundaries in the subscale area during the corrosion process.     

Characterisation of electrochemical interactions between single phases of Nd‐Fe‐B permanent magnets

The electrode functions (anode or cathode) of coupled single phases (ferromagnetic phase: Nd₂Fe₁₄B; boron rich phase: Nd_1+εFe₄B₄; neodymium rich phase: Nd₄Fe) of Nd‐Fe‐B permanent magnets have been investigated. The electrochemical potential differences and current densities between the three phases were determined. Furthermore, the corrosion current density of the magnetic materials in 0.1 M H₂SO₄ was calculated from measurements of current density‐potential curves. The neodymium rich phase works as the anode in contact with both the ferromagnetic and the boron rich phase. The calculation of corrosion current densities for systems of three coupled phases from the current density‐potential curves of single phases measurements demonstrates very high values for the small area of the corroding neodymium rich phase at the grain boundaries. An increase of corrosion resistance of Nd‐Fe‐B‐magnets is possible only by an increase of the corrosion resistance of neodymium rich phase. The presented results do not demonstrate an important influence of the alloying elements gallium or dysprosium on the corrosion rate of the Nd‐Fe‐B magnets. Therefore, new concepts have to be developed to increase the corrosion resistance of these magnets.     

The corrosion behavior of amorphous and nanocrystalline Fe73.5Cu1Nb3Si15.5B7 alloy

The potentiodynamic polarization curves in 0.5 M NaCl solution before and after crystallization of Fe_73.5Cu₁Nb₃Si_15.5B₇ alloy have been studied in relation to the microstructure and alloy composition. It was shown that the corrosion resistance of the alloy strongly depending on these two factors. The observed decrease in corrosion resistance of the alloy after the heat treatment up to 480 °C in comparison to the corrosion resistance of the alloy in the as prepared state is attributed to the increased inhomogeneity of the alloy that coincides with the first appearance of Fe₃Si phase. Further heating (up to 600 °C) resulted in an increase in the number of Fe₃Si nanocrystallites and the appearance of a FeCu₄ phase. After annealing at 600 °C the lowest corrosion rate, 0.004 mm a⁻¹, was observed. Annealing of the samples at higher temperatures (>600 °C) induced formation of six crystalline phases which proved detrimental to the corrosion resistance of the Fe_73.5Cu₁Nb₃Si_15.5B₇ alloy. Solid corrosion products were identified on the surface of the samples after anodic polarization.     

Solution chemistry of Mo(III) and Mo(IV): Thermodynamic foundation for modeling localized corrosion

To investigate the behavior of molybdenum dissolution products in systems that approximate localized corrosion environments, solubility of Mo(III) in equilibrium with solid MoO₂ has been determined at 80 °C as a function of solution acidity, chloride concentration and partial pressure of hydrogen. The measurements indicate a strong increase in solubility with acidity and chloride concentration and a weak effect of hydrogen partial pressure. The obtained results have been combined with literature data for systems containing Mo(III), Mo(IV), and Mo(VI) in solutions to develop a comprehensive thermodynamic model of aqueous molybdenum chemistry. The model is based on a previously developed framework for simulating the properties of electrolyte systems ranging from infinite dilution to solid saturation or fused salt limit. To reproduce the measurements, the model assumes the presence of a chloride complex of Mo(III) (i.e., MoCl²⁺) and hydrolyzed species (MoOH²⁺, Mo(OH)₂⁺, and Mo(OH)₃⁰) in addition to the Mo³⁺ ion. The model generally reproduces the experimental data within experimental scattering and provides a tool for predicting the phase behavior and speciation in complex, concentrated aqueous solutions. Thus, it provides a foundation for simulating the behavior of molybdenum species in localized corrosion environments.     

Interfacial morphology and corrosion resistance of Fe–B cast steel containing chromium and nickel in liquid zinc

The interfacial morphology and corrosion resistance of low carbon Fe–B cast steels in zinc bath at 520 °C were investigated. The results show Fe–B cast steel containing high Cr and Ni exhibits the best corrosion resistance to liquid zinc. The corrosion layers are composed of Γ-Fe₃Zn₁₀, δ-FeZn₁₀, ξ-FeZn₁₃ and η-Zn. The corrosion behaviour of Fe–B cast steels includes the following processes: the preferential leach and dissolution of Cr and Ni, the formation of Fe–Zn compounds controlled by zinc atom diffusion, and the spalling of borides without the supporting role of α-(Fe, Cr) matrix corroded by liquid zinc.     

Electrochemical corrosion behavior of Mg-5Al-0.4Mn-xNd in NaCl solution

The electrochemical corrosion behavior of Mg-5Al-0.4Mn-xNd (x = 0, 1, 2 and 4 wt.%) alloys in 3.5% NaCl solution was investigated. The corrosion behavior of the alloys was assessed by open circuit potential measure, potentiodynamic polarization, and electrochemical impedance spectroscopy. The electrochemical results show the intermetallic precipitates with Nd behave as less noble cathodes in micro-galvanic corrosion and suppress the cathodic process. During corrosion, Al₂O₃ and Nd₂O₃, in proper ratio, is incorporated into the corrosion film, and enhances the corrosion resistance.     

Corrosion processes of Mg–Y–Nd–Zr alloys in Na2SO4 electrolyte

The corrosion behavior of Mg–Y–Nd–Zr (WE43 commercial alloy) was investigated in Na₂SO₄ electrolyte using potentiodynamic polarization curves, X-Ray Photoelectron Spectroscopy (XPS), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) depth profiles, Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectrometry (EDS) analyzes. SEM and EDS data show that Nd-rich precipitates are mainly located at the grains boundaries. Zr/Y-rich zones are distributed inside the most of the grains. XPS study indicates a depletion of Mg on surface that could be attributed to Mg dissolution and an enrichment of the addition element oxides. XPS and ToF-SIMS analyzes demonstrate that the corrosion films are made up of a magnesium hydroxide (Mg(OH)₂) outer layer and an inner layer containing magnesium oxide (MgO), yttrium oxide (Y₂O₃) and hydroxide (Y(OH)₃), mixed with a small amount of MgH₂, zirconium oxide (ZrO₂) and neodymium oxide (Nd₂O₃). The Y₂O₃ and Y(OH)₃ signals increase slightly in the inner layer towards the corrosion film/alloy interface. Unlike these compounds, ZrO₂ and Nd₂O₃ compound signals are constant inside the inner layer. It is concluded that: (i) neodymium, zirconium and yttrium play a key role in the slightly improved corrosion resistance of the alloy and (ii) the cathodic reaction is slower on WE43 than on pure Mg and AZ91.     

CRYSTALLIZATION PROCESS AND NON–ISOTHERMAL CRYSTALLIZATION KINETICS OF MELT–SPUN Nd–Fe–B AMORPHOUS THICK RIBBONS

利用熔体快淬法在12 m/s的辊速下制备了Nd₆Fe₇₂B₂₂和Nd₆Fe₆₈Ti₄B₁₇C₅非晶厚带. 通过DSC和XRD, 并借助Kempen模型和 Kissinger方程, 研究了合金的非晶晶化过程及非等温晶化动力学. 结果表明, 两种合金厚带具有不同的晶化过程以及晶化动力学机制. Nd₆Fe₇₂B₂₂合金的晶化过程分为三步完成: 非晶
相 (AP)→ Nd₂Fe₂₃B₃→Nd₂Fe₁₄B+ α--Fe +Fe₃B→Nd₂Fe₁₄B+α--Fe+Fe₃B+NdFe₄B₄, 而Nd₆Fe₆₈Ti₄B₁₇C₅ 合金一步完成晶化: AP→Nd₂(Fe, Ti)₁₄(B, C)+α--Fe + Fe₃B. 与Nd₆Fe₇₂B₂₂合金由界面控制的多晶型晶化不同, Nd₆Fe₆₈Ti₄B₁₇C₅合金以扩散控制的共晶型晶化为主.     

Thermally induced decomposition of B4C barrier layers in Mo/Si multilayer structures

We investigate the influence of the Mo crystalline state (quasi-amorphous or crystalline) on the thermal stability of Mo/Si thin film multilayers with B₄C diffusion barrier layers at either of the two interfaces. We find that multilayers containing amorphous Mo layers are more stable than those containing crystalline layers. This observation is in contrast to the case where Si₃N₄ diffusion barriers are used. Using X-ray diffraction, X-ray reflection and X-ray photo-electron spectroscopy we show that this difference can be attributed to the dissociation of B₄C followed by diffusion of B in Mo. Due to the favorable thermodynamic properties of Mo_xB_y compounds, the boron atoms react with the Mo layer, forming a Mo_xB_y layer that effectively improves the multilayer thermal resistance.     

Grain boundary and interface chemistry of an Nd-Fe-B-based sintered magnet

The compositions of grain boundaries (GBs) and other interfaces surrounding Nd₂Fe₁₄B grains in commercial Nd-Fe-B sintered magnets have been investigated by laser-assisted three-dimensional atom probe to understand the mechanism of the coercivity enhancement by post-sinter annealing. While only a slight segregation of Nd and Pr to the GBs was confirmed in the as-sintered sample, a thin Nd-rich amorphous phase layer was observed along the GBs with Cu segregation to the interfaces in the annealed sample. The segregation of Cu to NdO_x/Nd₂Fe₁₄B interfaces was also found, suggesting that the Nd₂Fe₁₄B grains are enveloped by a Cu-enriched layer after the annealing. The concentration of Fe + Co in the thin GB layer was found to be as high as 65 at.%, and a model amorphous film processed by sputtering with the same composition as the thin GB layer was found to be ferromagnetic. Ferromagnetic behavior of the thin GB layer suggested that Nd₂Fe₁₄B grains are magnetically coupled. The coercivity mechanism of the sintered magnets is discussed based on these new findings.     

Corrosion behaviour of a 2219 aluminium alloy treated with a chromate conversion coating exposed to a 3.5% NaCl solution

This study investigates the formation of a chromate conversion coating at Al–Cu–Fe–Mn intermetallic sites of an Al2219 alloy and the corrosion initiation at these sites in a 3.5% NaCl solution, using SEM, AES and EDX. Changes in the surface chemistry were monitored after progressive exposures to the solution up to 42 h. The coating was found to be thinner and more defective on the intermetallic. Initially, Al is dissolved and Al(OH)₃ deposited on and around the intermetallic. After 42 h of exposure, Al(OH)₃, Fe and Mn oxides and small particles of elemental Cu are deposited as corrosion products.     

A comparative study on the corrosion behavior of NdFeB magnets in different electrolyte solutions

Sintered NdFeB magnets possess excellent magnetic properties. However, the corrosion resistance property of NdFeB is very poor due to its multiphase microstructure consisting of matrix phase Nd₂Fe₁₄B, Nd‐rich phase, and B‐rich phase. The corrosion behavior of NdFeB magnets in sodium hydroxide (NaOH), sodium chloride (NaCl), nitric acid (HNO₃), and oxalic acid (H₂C₂O₄) solutions was investigated by immersion and electrochemical tests. HNO₃is the strongest corrosive electrolyte compared with the other three solutions. The increase in HNO₃concentration can accelerate the corrosion of NdFeB magnets. NaCl belongs to medium corrosion electrolyte. A NaCl concentration of 0.5 M shows the severest corrosive feature in comparison with other concentrations of NaCl solution. NdFeB hardly suffers corrosion in NaOH and H₂C₂O₄solutions owing to the formation of passivation films on the surface of magnets. Based on the corrosion behavior of NdFeB in different electrolytes, the possible corrosion mechanisms are discussed.     

The corrosion resistance of a Fe/Cu composite

A composite made from a mixture of iron and copper powders was produced and characterised. The Cu addition favours the production of sintered Fe in the powder metallurgy industry processes. The corrosion behaviour in different electrolytic solution (sodium chloride or hydrochloric, acetic or sulphuric acids) and the corrosion rates were obtained from the weight loss and potentiodynamic methods – intersection and linear polarisation resistance. The values in hydrochloric and sulphuric acid vary slightly with respect to the average value of 78 mV/decade. The values obtained in acetic acid and sodium chloride are higher probably due to the formation of a thin film layer over the metallic surface. The morphology was analyzed through the observation by optical and scanning electron microscopy. It has been determined the nature of the oxide layer, Fe₃O₄, by X‐ray photoelectron spectroscopy (XPS), isolating the composite from the atmosphere. Thus, this oxide layer acts as a corrosion protective surface.     

An ESEM in situ investigation of initial stages of the KCl induced high temperature corrosion of a Fe–2.25Cr–1Mo steel at 400 °C

The initial oxidation of a low-alloyed steel (Fe–2.25Cr–1Mo) in the presence of small amounts of KCl(s) have been investigated through ESEM in situ exposure and analysis at 400 °C. The samples were also characterized by XRD, SEM/EDX and FIB. The present study shows the corrosive nature of KCl towards the low alloyed steel. It is concluded that the initial KCl distribution is important and that a KCl/FeCl₂ liquid phase film forms on large parts of the oxide surface in the presence of KCl. It is proposed that Cl increases the oxidation rate (by decorating oxide grain boundaries) and decreases the oxide scale adhesion.     

Mo microalloying effect on the glass-forming ability, magnetic, mechanical and corrosion properties of (Fe0.76Si0.096B0.084P0.06)100-xMox bulk glassy alloys

The effect of Mo addition on the glass-forming ability (GFA), magnetic properties, mechanical properties and corrosion resistance of (Fe_0.76Si_0.096B_0.084P_0.06)_100−xMo_x (x = 0, 2, 4 and 6 at.%) bulk glassy alloys (BGAs) with high Fe contents was investigated. The 2 at.% Mo addition makes the alloy composition approach towards a eutectic point, which could result in an increase in the GFA. The BGA rod with diameters up to 3.5 mm was produced by copper mold casting. These BGAs exhibit a rather high saturation magnetization of 0.98-1.51 T and lower coercive force of 1.7-2.1 A/m. A significant improvement in corrosion resistance was observed with microalloying Mo element in 1 N H₂SO₄ solution. Furthermore, these Fe-based BGAs show super-high strength of ∼3.3 GPa and Young's modulus of 200 GPa.     

Fe-based soft magnetic amorphous alloys with high saturation magnetization above 1.5 T and high corrosion resistance

Fe-rich amorphous alloys with minor-addition of Cr and/or Nb were examined with the aim of developing Fe-based amorphous alloys exhibiting simultaneously high saturation magnetization above 1.5 T and good corrosion properties. Fe₈₂Cr₂B₈P₄Si₃C and Fe₈₂NbB₉P₄Si₃C amorphous alloys were found to exhibit high saturation magnetizations of 1.49 T and 1.57 T, respectively, and rather good corrosion resistance in 3.5 mass% NaCl solution at 298 K. The minor-addition of Cr or Nb enables the formation of amorphous alloy particles without harmful oxide layer by water atomization process which makes these alloys suitable for applications as soft magnetic core materials. The addition of 1 at% Nb improved the corrosion resistance through the increase in E_corr value, which makes easy to reach passive state, and the suppression of pitting corrosion. Besides, it has been proved that the simultaneous addition of Nb and Cr has an effect on forming protective passive film.     

Corrosion characteristics of LiBH4 film exposed to a CO2/H2O/O2/N2 mixture

LiBH₄ films were prepared by pulsed laser deposition using a LiB target in a background pressure of hydrogen. The corrosion characteristics of LiBH₄ films were measured by exposing them to a gas mixture of CO₂/H₂O/O₂/N₂ at ambient temperature for 1–24 h. Scanning electron microscopy images show some cracks on the surface of corrosion films, which could act as easy paths for H₂O and CO₂ to further react with Li⁺ and B³⁺. The X-ray photoelectron spectroscopy results and theoretical analysis show that LiBH₄ tends to react with H₂O and CO₂ to form Li₂B₄O₇, Li₂CO₃ and LiOH during the corrosion process.