Proven Anti-Wetting Properties of Molybdenum Tested for High-Temperature Corrosion-Resistance with Potential Application in the Aluminum Industry
Abstract
:1. Introduction
- The use of modelling to predict and demonstrate the anti-wetting properties of bulk Mo in contact with molten Al;
- Provide experimental proof of the anti-stick properties of metallic Mo in a molten Al alloy using the ALCAN standard immersion test, thus leading to a potential application in the Al industry;
- The application of radio frequency (RF) suspension plasma-spray (SPS) technology in synthesizing high-density Mo-based coatings, a process that cannot be easily achieved due to Mo’s high melting point at 2896 K (2623 °C).
2. Materials and Methods
2.1. Modelling as a Predictive Tool
2.1.1. Simulation by FactSage™
2.1.2. Simulation Using Classical Molecular Dynamics
2.2. Surface Energy Determination
2.3. The ALCAN Standard Immersion Test
2.4. Materials Characterization
2.4.1. Optical Microscopy
2.4.2. Elemental Analysis by Optical Emission Spectrometry (OES)
2.4.3. Scanning Electron Microscopy (SEM)
2.4.4. X-ray Diffraction (XRD)
3. Results
- (a)
- Computer simulation results, which indicate that modelling as a predictive tool using both FactSage™ thermochemical software and Classical Molecular Dynamics showed that there would be no reaction and atomic diffusion at the interface between the Mo block and the molten Al alloy. The estimation of the surface energy by the VCG theory using the sessile drop experiments equally predicted a weak surface interaction at the Mo(s)–Al(l) interface.
- (b)
- Experimental data from the static ALCAN immersion test agree with the simulation results, although some traces of Al-Mo alloys were detected on the Al-rich side of the Mo(s)–Al(l) interface. A weak interaction existed between the Al-Mo alloys and the solid Mo block (Mo-rich side), making it easy for Mo to peel off and demonstrate its anti-wetting properties; we suspect that the 20% mass loss on Mo was due to the chemical attack along the grain boundaries leading to intergranular corrosion.
3.1. Computer Modelling
3.1.1. Simulation by FactSage™
3.1.2. Simulation by Classical Molecular Dynamics
- (i)
- No cross diffusion of atoms at the Al–Mo interface was observed as no atoms of one element moved into the bulk of the other element;
- (ii)
- At the Al–Mo interface, Al formed a non-wetting layer adopting the morphology of the exposed Mo (100) crystal;
- (iii)
- The calculated mean surface (or interaction) energy at the Al–Mo interface was found to be ~203 mJ/m2 (at 1200 K).
3.2. Surface Energy Determination
3.3. The Static ALCAN Immersion Test
3.3.1. Mass Loss Analysis
3.3.2. Analysis of Anti-Wetting Properties through Optical Microscopy
3.3.3. SEM Analysis at the Mo/Al-Mg Interface
3.4. Materials Characterization
3.4.1. Elemental Analysis by OES
3.4.2. SEM Analysis
3.4.3. XRD Analysis
4. Discussion
4.1. Modelling Material Properties
4.2. The ALCAN Immersion Test and Application in the Al Industry
- (i)
- While their tests were conducted at 800 °C and below, in this work, the static ALCAN immersion test was performed at 850 °C, with only small quantities of the Al-Mo alloys being observed at the Mo(s)–{Al-Mg}(l) interface;
- (ii)
- Contrary to their case where the Al-Mo alloys formed were known, in the present work, elemental analysis identifying the type of Al-Mo alloys present at the the Mo(s)–{Al-Mg}(l) interface was difficult since the alloys were extremely thin and not cross-sectionally visible at the interface (Figure 13);
- (iii)
- The mass loss of ~20% observed in the Mo block in this work was not principally as a result of the reaction between Mo and the molten Al-Mg alloy, but rather due to intergranular corrosion at the grain boundaries chipping away at the Mo block over time;
- (iv)
- Although modelling by FactSage™ thermochemical software predicted the potential formation of Al4Mo, Al5Mo, and Al8Mo3 alloys when molten Al-Mg alloy is in contact with Mo, kinetically these alloys would form very slowly. In addition, if the alloys formed around the Mo are insoluble in the molten Al-Mg alloy, they would create an impenetrable barrier that stops further reaction with Mo, which is beneficial to the process. Since it was not possible to detect Mo in the molten Al–Mg matrix using OES elemental analysis, it confirmed that, in this work, neither Mo nor the Al-Mo alloys dissolved in the molten Al-Mg alloy as was predicted by computer simulations using Classical Molecular Dynamics in the Materials Studio® packages.
5. Conclusions
- No reaction and no cross diffusion of atoms occurs at the Mo(s)–Al(l) interface;
- Molten Al atoms form a non-wetting layer that adopts an epitaxial orientation in alignment with the exposed solid Mo crystal morphology;
- The calculated mean interfacial energy normalized per unit area of the simulated cell was found to be about 203 mJ/m2, which implies a weak van der Waals interaction between molten Al and solid Mo.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Lattice Parameters | Before Melting | After Melting |
---|---|---|
a | 80.99 Å | 64.19 Å |
b | 80.99 Å | 62.00 Å |
c | 161.98 Å | 291.28 Å |
α | 90° | 89.29° |
β | 90° | 100.02° |
γ | 90° | 84.09° |
Metal Bonds | Bond Lengths (Å) | |
---|---|---|
Simulated Values (This Work) | Actual Data Values | |
Al-Al | 3.0 | 2.79 |
Al-Mo | 2.7 | 2.76 |
Mo-Mo | 2.7–3.1 | 2.09–3.27 |
Sample | Before Test | After Test | Loss (%) |
---|---|---|---|
Diameter (mm) | 44.28 | 41.27 | 6.80% |
Height (mm) | 25.44 | 24.78 | 2.59% |
Mass (g) | 396.30 | 315.13 | 20.48% |
Sampling | Al | Mg | Mo | Mn | Si | Fe | Total * |
---|---|---|---|---|---|---|---|
Before ALCAN test | 94.2 | 4.60 | 0.005 | 0.320 | 0.220 | 0.160 | 99.545 |
After ALCAN test | 95.700 | 2.890 | 0.012 | 0.370 | 0.360 | 0.160 | 99.492 |
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Gitzhofer, F.; Aluha, J.; Langlois, P.-O.; Barandehfard, F.; Ntho, T.A.; Abatzoglou, N. Proven Anti-Wetting Properties of Molybdenum Tested for High-Temperature Corrosion-Resistance with Potential Application in the Aluminum Industry. Materials 2021, 14, 5355. https://doi.org/10.3390/ma14185355
Gitzhofer F, Aluha J, Langlois P-O, Barandehfard F, Ntho TA, Abatzoglou N. Proven Anti-Wetting Properties of Molybdenum Tested for High-Temperature Corrosion-Resistance with Potential Application in the Aluminum Industry. Materials. 2021; 14(18):5355. https://doi.org/10.3390/ma14185355
Chicago/Turabian StyleGitzhofer, François, James Aluha, Pierre-Olivier Langlois, Faranak Barandehfard, Thabang A. Ntho, and Nicolas Abatzoglou. 2021. "Proven Anti-Wetting Properties of Molybdenum Tested for High-Temperature Corrosion-Resistance with Potential Application in the Aluminum Industry" Materials 14, no. 18: 5355. https://doi.org/10.3390/ma14185355