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.     

Comparison of the oxidation behaviour of WC–Co and WC–Ni–Co–Cr cemented carbides

Thermogravimetric experiments confirm that the oxidation resistance of WC–Co and WC–Ni–Co–Cr alloys increases with their metallic content. This is due to the fact that, as the metallic content increases, the oxide scales present higher MWO₄ to WO₃ ratios and lower porosity. The good correlation found between the activation energies calculated by either the isothermal or the isoconversion method suggests that oxidation is controlled by surface chemical reaction. Activation energies increase with temperature between 650 and 800 °C for both WC–Co and WC–Ni–Co–Cr alloys. This increment is higher for WC–Co materials due to their tendency to form scales with higher tungstate contents.     

High temperature oxidation behaviour of Ni–Fe–Co anodes for aluminium electrolysis

The oxidation behaviour of ternary Ni_xFe_yCo_z alloys (where x/y (wt) = 1 and 1.85; z = 0, 10, 30 and 50 wt.%) was studied in air at 800 °C. Alloys were found to follow complex oxidation kinetics, with the highest oxidation rates observed for alloys having 50 wt.% Co. Significant improvements in oxidation resistance were achieved by addition of 10 and 30 wt.% Co to the Ni–Fe system. The decrease in oxidation rate was associated with suppression of Fe₂O₃ formation in preference for (Co,Ni)_xFe_3−xO₄ growth. The results were discussed in light of the materials requirements for inert anodes for aluminium electrolysis.     

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.     

Synthesis and properties of open-cell Ni–Cr–Fe–Al alloy foams by pack co-deposition process

A pack cementation process for the co-deposition of Cr, Fe and Al onto open-cell nickel foam was developed. The reticulated open-cell Ni–Cr–Fe–Al foams were annealed to homogenize the material with 18.8 wt.% Cr, 11.3 wt.% Fe and 7.7 wt.% Al. The microstructure and phase composition of the Ni–Cr–Fe–Al foams were examined by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive analysis (EDS). The results show that the coating is uniform and dense along the perimeter of the Ni strut, and consists of three layers: a Cr–Fe outer layer, an inner layer containing mostly Al and a transition zone. After homogenization annealing, the alloyed foams retain the hollow struts structure of the original pure nickel foams and the low relative densities. The Ni–Cr–Fe–Al alloy foams exhibit enhancement in absolute strength as compared to the pure nickel and Ni–35.2Cr foams. Furthermore, the Ni–Cr–Fe–Al alloy foams show excellent oxidation resistance and outperform the chromia-forming Ni–35.2Cr alloy foam after oxidation at 900 and 1000 °C, which is mainly due to its high aluminum and chromium content leading to the formation of a continuous and adherent duplex oxide layer.     

Corrosion of nanocrystalline Ni–W alloys in alkaline and acidic 3.5 wt.% NaCl solutions

The corrosion behaviour of reverse-pulse electrodeposited nanocrystalline nickel tungsten alloys (nc Ni–W) in pH 3 and 10 3.5 wt.% NaCl solutions is investigated and analysed as a function of grain size. A potentiodynamic polarisation study reveals that the corrosion rate of nc Ni–W generally increases with the reduction of grain size in alkaline condition, but decreases with the reduction of grain size in acidic environment. Furthermore, for both environments, nc Ni–W alloys exhibit superior localised corrosion resistance than a microcrystalline Ni control specimen. Factors controlling the corrosion behaviour of these materials, including grain size, tungsten content, passivation and crystallographic texture are addressed.     

The effect of Al content on the galvanic corrosion behaviour of coupled Ni/graphite and Ni–Al coatings

In this study, the corrosion behaviour of 75Ni/25graphite abradable coating and Ni–Al bonding coatings with different Al content were investigated with open circuit potential and polarization tests. The galvanic corrosion of the coupled Ni/graphite and Ni–Al coatings was studied by using a zero-resistance ammeter in 5 wt% NaCl solution. The experimental results showed that the corrosion resistance of the Ni–Al coatings decreased with increasing Al contents. In the galvanic corrosion test, the Ni–Al coatings with high Al contents (80Ni–20Al, 85Ni–15Al, and 90Ni–10Al) were the anodic element of the couples, while, the 95Ni–5Al acted as the cathode element in the couple.     

Effect of Cr, Yb and Zr additions on localized corrosion of Al–Zn–Mg–Cu alloy

The effect of Cr, Yb and Zr additions on localized corrosion of Al–Zn–Mg–Cu alloy has been investigated. Additions of Cr, Yb and Zr to Al–Zn–Mg–Cu alloy stabilized the deformation-recovery microstructure with low angle grain boundaries on which grain boundary precipitates distributed discretely. The exfoliation and stress corrosion cracking of Al–Zn–Mg–Cu alloys propagated along the high angle recrystallized grain boundaries. The unrecrystallized Al–Zn–Mg–Cu–Zr–Cr–Yb alloy exhibited higher resistance to stress corrosion cracking and exfoliation corrosion, compared to the partial recrystallized Al–Zn–Mg–Cu–Zr alloy with high angle grain boundaries.     

Metal release from stainless steel, Co–Cr–Mo–Ni–Fe and Ni–Ti alloys in vascular implants

A seven-day immersion test using several solutions was conducted on stainless steel, Co-based alloy, and Ni–Ti alloy, which are used for stents and stent grafts. The quantitative data on the release of each metal ion and the correlation between metal ion release rate and pH were obtained. The quantities of Fe and Ni released from stainless steel gradually decreased with increasing solution pH (pH 2–7.5). For Co–Cr–Mo–Ni–Fe alloy, the quantity of Cr released steadily increased as pH decreased (pH ≤ 6) and reached nearly zero at pHs higher than 6 (pH 6–7.5). Co release was slightly affected by a variation in pH. The quantities of Ni and Ti released from Ni–Ti alloy markedly increased with decreasing pH (pH ≤ 4) and they leveled off from pH 4 (pH 4–7.5). Although the rapid increases were observed at approximately pH 2, the quantities were even higher than that of Co released from the Co–Cr–Mo and Co–Cr–Mo–Ni–Fe alloys. For further investigation of the rapid increase in the quantities of metals released at pH 2, an anodic polarization test was employed to study the passive and transpassive behaviours of Ni–Ti alloy. The critical current density for the passivation of Ni–Ti alloy markedly increased as pH decreased (pH ≤ 4) and was low (1.4 μA/cm²) at pH higher than 4 (pH 4–7.5). The potential at a current density of 10 μA/cm², by contrast, markedly rose with decreasing pH (pH ≤ 2), and was 1.2 V from pH 2 (pH 2–7.5).     

Carburisation of ferritic Fe–Cr alloys by low carbon activity gases

Model Fe–Cr alloys were exposed to Ar–CO₂–H₂O gas mixtures at 650 and 800 °C. At equilibrium, these atmospheres are oxidising to the alloys, but decarburising (a_C ≈ 10⁻¹⁵ to 10⁻¹³). In addition to developing external oxide scales, however, the alloys also carburised. Carbon supersaturation at the scale/alloy interface relative to the gas reflects local equilibrium: a low oxygen potential corresponds to a high p_CO/p_CO2 ratio, and hence to a high carbon activity. Interfacial carbon activities calculated on the basis of scale–alloy equilibrium are shown to be in good agreement with measured carburisation rates and precipitate volume fractions, providing support for the validity of the thermodynamic model.     

On the oxidation mechanism of Ni–Pt alloys at high temperatures

The oxidation mechanism of Ni–Pt alloys has been studied as a function of alloy composition, oxygen pressure and temperature. It has been found that the oxidation rate of all the alloys follows the parabolic rate law, being thus diffusion controlled. In agreement with Wagner’s theory, the slowest step of the overall oxidation rate of alloys with higher nickel content (?40 at.%) is determined by the outward diffusion of nickel cations in the growing NiO scale. On the other hand, the oxidation rate of alloys with a lower nickel content (<40 at.%) is governed by the solid state diffusion in the metallic phase.     

Oxide networks, graph theory, and the passivity of Ni–Cr–Mo ternary alloys

The passivity of Ni–Cr–Mo ternary alloys is considered in terms of a continuous network of –Cr–O–Cr– bridges in the oxide film (which also contains Ni²⁺ and Mo⁴⁺ ions), or in terms of a continuous network of –Ni–O–Ni– bridges in the oxide film (which also contains Cr³⁺ and Mo⁴⁺ ions). The structure of the oxide is represented by a mathematical graph, and graph theory is used to calculate the connectivity of the oxide. This approach shows that a continuous network of –Cr–O–Cr– bridges occurs when the cation fraction of Cr³⁺ ions in the oxide is 0.35 or greater. A continuous network of –Ni–O–Ni– bridges occurs when the cation fraction of Ni²⁺ ions in the oxide is 0.55 or greater. Experimental results support the –Cr–O–Cr– model.     

Wear and corrosion behaviour of Ti–13Nb–13Zr and Ti–6Al–4V alloys in simulated physiological solution

Wear and corrosion behaviour of cold-rolled Ti–13Nb–13Zr alloy, with martensitic microstructure, and Ti–6Al–4V ELI alloy, in martensitic and two-phase (α + β) microstructural conditions, was studied in a Ringer’s solution. The wear experiments were performed at room temperature with a normal load of 40 N and sliding speeds 0.26, 0.5 and 1.0 m/s. The corrosion behaviour was studied at 37 °C using open circuit potential-time measurements and potentiodynamic polarization. It was found that Ti–13Nb–13Zr alloy has a substantially lower wear resistance than Ti–6Al–4V ELI alloy in both microstructural conditions. Surface damage extent increases with sliding speed increase and is always smallest for martensitic Ti–6Al–4V ELI alloy with highest hardness. Both alloys exhibit spontaneous passivity in Ringer’s solution. Corrosion potential values are similar for all three materials. However, Ti–13Nb–13Zr and martensitic Ti–6Al–4V ELI alloys show improved corrosion resistance comparatively to Ti–6Al–4V ELI alloy with (α + β) microstructure. Martensitic Ti–6Al–4V ELI alloy possesses the best combination of both corrosion and wear resistance, although its corrosion resistance is found to be slightly higher than that of the Ti–13Nb–13Zr alloy.     

Influence of Cr Content on the Corrosion of Fe–Cr Alloys: The Synergistic Effect of NaCl and Water Vapor

The corrosion behavior of pure Fe and Fe–Cr alloys with different Cr content in the presence of a solid NaCl deposit and water vapor at 600°C was studied. Results indicated that the corrosion of pure Fe was severe even in air at 600°C and the scale formed on the surface was compact and uniform. However, with a solid NaCl deposit on its surface, the corrosion of pure iron in air was suppressed to some extent, but the presence of water vapor in the atmosphere causes accelerated corrosion. Under the synergistic effect of NaCl and water vapor, the corrosion of pure iron is accelerated more significantly. In contrast with the known effect of Cr content on the oxidation of Fe–Cr alloys, an increasing Cr content in Fe–Cr alloys increases the corrosion rate of the alloys under the synergistic effect of solid NaCl and water vapor. A mechanism to explain the effect of water vapor and NaCl on the corrosion of pure iron and Fe–Cr alloy is proposed.     

Fe–C-coated fibre Bragg grating sensor for steel corrosion monitoring

A steel corrosion sensor based on fibre Bragg gratings (FBGs) has been developed and tested in this paper. The steel corrosion sensor has been formed by electroplating a Fe–C film on a metallized FBG. The coated FBG sensors have been tested in cabinets in which the availability of chloride ions and oxygen are controlled. The microstructural changes have been investigated by optical microscopy and SEM imaging. The FBG spectra are collected by a spectrometer. The results show that the spectra change, the wavelength shift, and the occurrence of multiple peaks are related to the corrosion degree of the Fe–C film.     

The third-element effect in the oxidation of Ni–xCr–7Al (x = 0, 5, 10, 15 at.%) alloys in 1 atm O2 at 900–1000 °C

The oxidation in 1 atm of pure oxygen of Ni–Cr–Al alloys with a constant aluminum content of 7 at.% and containing 5, 10 and 15 at.% Cr was studied at 900 and 1000 °C and compared to the behavior of the corresponding binary Ni–Al alloy (Ni–7Al). A dense external scale of NiO overlying a zone of internal oxide precipitates formed on Ni–7Al and Ni–5Cr–7Al at both temperatures. Conversely, an external Al₂O₃ layer formed on Ni–10Cr–7Al at both temperatures and on Ni–15Cr–7Al at 900 °C, while the scales grown initially on Ni–15Cr–7Al at 1000 °C were more complex, but eventually developed an innermost protective alumina layer. Thus, the addition of sufficient chromium levels to Ni–7Al produced a classical third-element effect, inducing the transition between internal and external oxidation of aluminum. This effect is interpreted on the basis of an extension to ternary alloys of a criterion first proposed by Wagner for the transition between internal and external oxidation of the most reactive component in binary alloys.     

High-temperature oxidation of Fe-Cr-Al-Si alloys extruded into honeycomb structures

The oxidation behavior of Fe–20Cr–5Al–(0.5–5)Si and Fe–(12–20)Cr–(5–7)Al–(1–2)Si alloys extruded into honeycomb structures has been investigated at 1150°C in air for up to 500 hr. The oxidation weight gains decrease with increasing Si and Cr contents in the 5-Al alloys. Si additions are more efficient than Cr additions to reduce the weight gain. Increasing Si content in the 5-Al alloys suppresses the formation of an iron-chromium complex oxide, forming mullite and vitreous silica in the scale, although the location is not clearly indicated. The 5-Si alloy shows anisotropy in elongation of the honeycomb specimen during oxidation in the Fe–20Cr–5Al–xSi alloys, whereas alloying with Si and Cr does not improve the oxidation resistance of the 7-Al alloys significantly. These results are explained by Wagner's theory of a secondary getter. However, we point out additionally that the difference between Si and Cr in the Pilling-Bedworth ratio and the solubility of their oxides in the Al₂O₃ scale may contribute to the significant effect of Si additions. Finally, this paper demonstrates that the selected Fe–Cr–Al–Si honeycombs having walls 200 m thick show excellent oxidation resistance over 500 hr at 1150°C in air. The time to catastrophic oxidation is roughly proportional to the wall thickness in extruded honeycombs.     

A MICROSCOPIC PHASE–FIELD STUDY FOR THE INFLUENCE OF ORDERING ENERGY ON Cr SUBSTITUTION BEHAVIOR IN Ni75Al15Cr10 ALLOY

通过微观相场方法研究了Ni₇₅Al₁₅Cr₁₀合金在1073 K时效时, 不同原子间有序能下Cr原子的替代行为. 结果表明, 在γ'有序相中, 同时存在Ni--Al原子反位和Cr原子对Ni和Al原子的替代行为, 其中以替代行为为主; 随着第1,3层Ni--Al和Ni--Cr有序能的增大, Cr原子替代Al位的趋势增大, 替代Ni位的趋势减小; 第2, 4层Ni--Al和Ni--Cr有序能增大时, Cr原子替代Ni位的趋势增大, 替代Al位的趋势减小; 第1, 3层Al--Cr有序能增大时, Cr替代Ni位的趋势增大, 替代Al位的趋势减小; 第2, 4层Al--Cr有序能增大时, Cr替代Ni位的趋势减小, 替代Al位的趋势增大.     

High temperature scaling of Ni-xSi-10 at.% Al alloys in 1 atm of pure O2

The oxidation of Ni-xSi-10Al alloys (with x = 0, 2, 4 and 6 at.%), has been studied at 900 and 1000 °C in 1 atm of pure O₂ to examine the effect of different silicon additions on the behavior of ternary Ni-Si-10Al alloys. The kinetic curves of Ni-10Al are approximately parabolic at both 900 and 1000 °C. Conversely, the kinetics of the ternary alloys at both temperatures correspond generally to a rate decrease faster than predicted by the parabolic rate law, except for the oxidation of Ni-6Si-10Al at 1000 °C, which exhibits a single nearly-parabolic stage. Oxidation of the binary alloy formed at both temperatures an internal oxidation zone beneath a layer of NiO. Oxidation of Ni-2Si-10Al at both temperatures and of the other two alloys at 900 °C formed initially a zone of internal oxidation of Al + Si. However, a layer of alumina forming at the front of internal oxidation after some time blocked the internal oxidation and produced a gradual conversion of the metal matrix of this region into NiO, with a simultaneous decrease of the oxidation rate. Conversely, the oxidation of Ni-4Si-10Al and Ni-6Si-10Al at 1000 °C did not produce an internal oxidation, but formed an alumina layer directly on the alloy surface after an initial stage when also Ni was oxidized. Therefore, silicon exerts the third-element effect by reducing the critical Al content needed for the transition from its internal to its external oxidation with respect to the corresponding Ni-Al alloy. This result is interpreted by means of an extension to ternary alloys of Wagner’s criterion for the same transition in binary alloys based on the attainment of a critical volume fraction of internal oxide.     

The nature of the third-element effect in the oxidation of Fe-xCr-3 at.% Al alloys in 1 atm O2 at 1000 °C

The oxidation of an Fe-Al alloy containing 3 at.% Al and of four ternary Fe-Cr-Al alloys with the same Al content plus 2, 3, 5 or 10 at.% Cr has been studied in 1 atm O₂ at 1000 °C. Both Fe-3Al and Fe-2Cr-3Al formed external iron-rich scales associated with an internal oxidation of Al or of Cr+Al. The addition of 3 at.% Cr to Fe-3Al was able to stop the internal oxidation of Al only on a fraction of the alloy surface covered by scales containing mixtures of the oxides of the three alloy components, but not beneath the iron-rich oxide nodules which covered the remaining alloy surface. Fe-5Cr-3Al formed very irregular external scales where areas covered by a thin protective oxide layer alternated with others covered by thick scales containing mixtures of the oxides of the three alloy components, undergrown by a thin layer rich in Cr and Al, while internal oxidation was completely absent. Conversely, Fe-10Cr-3Al formed very thin, slowly-growing external Al₂O₃scales, providing an example of third-element effect (TEE). However, the TEE due to the Cr addition to Fe-3Al was not directly associated with a prevention of the internal oxidation of Al, but rather with the inhibition of the growth of external scales containing iron oxides. This behavior has been interpreted on the basis of a qualitative oxidation map for ternary Fe-Cr-Al alloys taking into account the existence of a complete solid solubility between Cr₂O₃ and Al₂O₃.