Corrosion-Resistant High-Entropy Alloys: A Review
Abstract
:1. Introduction
2. Review
2.1. Environmental and Alloying Effects on Corrosion Behavior
2.1.1. Corrosion Behavior in Chloride-Containing Solutions
2.1.2. Corrosion Behavior in Acid Solutions
2.1.3. Corrosion Behavior in High-Temperature High-Pressure Water
2.2. Corrosion Resistance of HEA Coatings
2.2.1. Coating by Laser Cladding
2.2.2. Coating by Magnetron Sputtering
2.3. Heat-Treatment Effect
2.4. Comparison between HEAs and Conventional Alloys
3. Discussion
4. Suggested Future Work
- For the aspect of the comprehensive characterization of corrosion behavior, high-resolution observation of the oxide film formation during the electro-corrosion test should be carried out. The features of HEAs are the disordered chemical environment and the usually formed nanoscale participates due to the slow diffusion rate of the elements. However, the current research results mainly provide microscale characterization and cannot explain the basic reason behind why HEAs possess novel corrosion-resistant properties. Thus, the high-resolution investigation, including the ex-situ and in-situ transmission electron microscopy (TEM) study of passive films, nanoscale atomic-force microscopy (AFM)/scanning transmission electron microscopy (STEM) observations, and depth-profile studies of passive films that have nano-thicknesses, could provide an atomistic understanding and is a prerequisite for the control of electrochemical surface processes.
- Since the homogenization of microstructures and elemental distributions can remarkably improve the corrosion resistance, a certain heat treatment and rapid cooling rate during the formation of coatings could improve the corrosion behavior through the attainment of uniform microstructures. However, guidance for the development of these uniform microstructures is absent. Therefore, both equilibrium and non-equilibrium thermodynamics calculations to predict the phase formation/transformation need to be conducted.
- Through coatings, firstly, the problem of the higher cost of HEAs could be resolved. Secondly, the satisfactory corrosion-resistant property could be retained with the addition of strengthening elements such as Al. Thus, insufficient mechanical properties that stop the HEAs from being used could be solved. Therefore, the study of how to synthesize high-quality HEA coatings is one of the major research directions for exploring the application of HEAs as corrosion-resistant materials. The effect of processing parameters and alloying should be taken into consideration.
- HEAs exhibit promising potential for applications in industry. However, the synergistic effects of service environments have not been widely considered, including the effects of residual stress, stress-corrosion cracking, and corrosion fatigue. Those investigations are indispensable for real-world applications.
5. Conclusions
- The surface passive films, which could provide the protection for the underlying alloys from dissolution, are of importance to the corrosion behavior. The additions of Al, Cu, Mo, and/or B increase the degree of elemental segregation, and lead to the formation of non-uniform passive films, which could induce galvanic corrosion or the localized break down of the passive films. Therefore, these elemental additions decrease the corrosion resistance in salt water and/or acid. In salt water, the anodic treatment, addition of Mo, and inclusion of the inhibitors could either improve the protection of the passive film or resist the penetration of Cl− anions, thus improving the corrosion resistance.
- Some HEAs possess novel corrosion behavior in high-temperature, high-pressure water environments, thus indicating that HEAs have the capacity of being applied in supercritical service environments.
- The HEA coatings synthesized by laser cladding, electro-spark deposition, and magnetron sputtering showed superior corrosion resistance. Attributed to the rapid-cooling process and high-entropy effect, the microstructure and elemental distribution of the coatings are more homogeneous than the bulk materials. The reduced formation of weak points in the passive film and galvanic cell improve the corrosion resistance.
- During the heat treatment of HEAs at elevated temperatures, the high-entropy effect would homogenize the microstructures and compositions, and remove the elemental segregations, therefore improving the corrosion resistance. However, the heat treatment temperature should be selected suitably under the guidance of phase formation rules to avoid the formation of undesired participates.
- The comparison of the corrosion behavior between HEAs and conventional alloys indicates that HEAs are good candidates as corrosion-resistant alloys in various aqueous environments. However, to gain an in-depth understanding of corrosion behavior, the high resolution observations of corrosion processes are suggested for future work. Moreover, the phase-formation rules under both equilibrium and non-equilibrium conditions need to be developed to guide the heat treatment and coating processes.
Acknowledgments
Conflicts of Interest
References
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Alloy | Solution | Ecorr 1 (VSHE 4) | icorr 2 (μA/cm2) | Epit 3 (VSHE) | Reference |
---|---|---|---|---|---|
CrFe1.5MnNi0.5 | 1 M NaCl | −0.39 | 0.45 | 0.019 | [41] |
Al0.3CrFe1.5MnNi0.5 | 1 M NaCl | −0.40 | 0.69 | −0.15 | [41] |
Al0.5CrFe1.5MnNi0.5 | 1 M NaCl | −0.50 | 1.02 | −0.12 | [41] |
FeCoNiCr | 0.6 M NaCl | −0.46 | 0.035 | 0.31 | [44] |
FeCoNiCrCu0.5 | 0.6 M NaCl | −0.49 | 0.72 | 0.09 | [44] |
FeCoNiCrCu | 0.6 M NaCl | −0.53 | 1.23 | 0.08 | [44] |
Co1.5CrFeNi1.5Ti0.5 | 1 M NaCl | −0.44 | 0.57 | 0.33 | [45] |
Co1.5CrFeNi1.5Ti0.5Mo0.1 | 1 M NaCl | −0.38 | 0.13 | 1.21 | [45] |
Co1.5CrFeNi1.5Ti0.5Mo0.5 | 1 M NaCl | −0.49 | 0.20 | 1.16 | [45] |
Co1.5CrFeNi1.5Ti0.5Mo0.8 | 1 M NaCl | −0.55 | 0.41 | 1.18 | [45] |
Alloy | Solution | Ecorr 1 (VSHE 4) | icorr 2 (μA/cm2) | ΔEb 3 (VSHE) | Reference |
---|---|---|---|---|---|
CrFe1.5MnNi0.5 | 0.5 M H2SO4 | −0.23 | 31.4 | 1.227 | [41] |
Al0.3CrFe1.5MnNi0.5 | 0.5 M H2SO4 | −0.19 | 73.9 | 1.176 | [41] |
Al0.5CrFe1.5MnNi0.5 | 0.5 M H2SO4 | −0.21 | 68.2 | 1.114 | [41] |
CoCrFeNi | 0.5 M H2SO4 | −0.081 | 15.8 | 1.098 | [42] |
Al0.25CoCrFeNi | 0.5 M H2SO4 | −0.095 | 16.7 | 1.092 | [42] |
Al0.5CoCrFeNi | 0.5 M H2SO4 | −0.084 | 13.4 | 1.083 | [42] |
AlCoCrFeNi | 0.5 M H2SO4 | −0.094 | 13.1 | 1.09 | [42] |
Co1.5CrFeNi1.5Ti0.5 | 0.5 M H2SO4 | −0.092 | 30 | 1.13 | [45] |
Co1.5CrFeNi1.5Ti0.5Mo0.1 | 0.5 M H2SO4 | −0.071 | 78 | 1.112 | [45] |
Co1.5CrFeNi1.5Ti0.5Mo0.5 | 0.5 M H2SO4 | −0.064 | 62 | 1.109 | [45] |
Co1.5CrFeNi1.5Ti0.5Mo0.8 | 0.5 M H2SO4 | −0.070 | 69 | 1.109 | [45] |
Cu0.5CrFeNiMn | 1 M H2SO4 | −0.073 | 20.9 | 0.050 | [48] |
CuCr0.5FeNi0.5Mn | 1 M H2SO4 | −0.090 | 40.2 | 0.035 | [48] |
Al0.5CoCrCuFeNi | 1 M H2SO4 | −0.115 | 78.7 | 0.348 | [50] |
Al0.5CoCrCuFeNiB0.2 | 1 M H2SO4 | −0.121 | 103 | 0.336 | [50] |
Alloy | Solution | Ecorr 1 (VSCE 3) | icorr 2 (μA/cm2) | Reference |
---|---|---|---|---|
AlCoCrFeNi | 0.05 M HCl | −0.55 | 29.2 | [52] |
Al1.3CoCrFeNi | 0.05 M HCl | −0.58 | 47.9 | [52] |
Al1.5CoCrFeNi | 0.05 M HCl | −0.92 | 31.4 | [52] |
Al1.8CoCrFeNi | 0.05 M HCl | −0.67 | 7.6 | [52] |
Al2CoCrFeNi | 0.05 M HCl | −0.66 | 3.7 | [52] |
Al2CrFeNiCoCu | 0.5 M HNO3 | −0.18 | 38 | [53] |
Al2CrFeNiCoCuTi0.5 | 0.5 M HNO3 | −0.30 | 22 | [53] |
Al2CrFeNiCoCuTi1 | 0.5 M HNO3 | −0.33 | 7.3 | [53] |
Al2CrFeNiCoCuTi1.5 | 0.5 M HNO3 | −0.30 | 4.4 | [53] |
Al2CrFeNiCoCuTi2 | 0.5 M HNO3 | −0.15 | 2.7 | [53] |
Al2CrFeCoCuTi | 0.6 M NaCl | −0.51 | 68 | [54] |
Al2CrFeCoCuTiNi0.5 | 0.6 M NaCl | −0.43 | 32 | [54] |
Al2CrFeCoCuTiNi1 | 0.6 M NaCl | −0.22 | 13 | [54] |
Al2CrFeCoCuTiNi1.5 | 0.6 M NaCl | −0.48 | 64 | [54] |
Al2CrFeCoCuTiNi2 | 0.6 M NaCl | −0.50 | 67 | [54] |
CoCrCuFeNi | 0.5 M H2SO4 | −0.32 | 21.9 | [55] |
AlCoCrFeNi | 0.6 M NaCl | −0.17 | 0.073 | [38] |
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Shi, Y.; Yang, B.; Liaw, P.K. Corrosion-Resistant High-Entropy Alloys: A Review. Metals 2017, 7, 43. https://doi.org/10.3390/met7020043
Shi Y, Yang B, Liaw PK. Corrosion-Resistant High-Entropy Alloys: A Review. Metals. 2017; 7(2):43. https://doi.org/10.3390/met7020043
Chicago/Turabian StyleShi, Yunzhu, Bin Yang, and Peter K. Liaw. 2017. "Corrosion-Resistant High-Entropy Alloys: A Review" Metals 7, no. 2: 43. https://doi.org/10.3390/met7020043