Low-Hysteresis Shape Memory Alloy Scale-Up: DSC, XRD and Microstructure Analysis on Heat-Treated Vacuum Induction Melted Ni-Ti-Cu-Pd Alloys
Abstract
:1. Introduction
2. Materials and Methods
3. Results
3.1. Group A Study—The Effect of Ti Content
3.2. Group B Study—The Effect of Pd Content
4. Discussion
5. Conclusions
- Homogenized VIM cast Ni-Ti-Cu-Pd alloys exhibit a non-equilibrium microstructure of a B2/B19 matrix phase with the unavoidable presence of secondary phases. XRD and microscopy analysis revealed the presence of different secondary phases in the melted ingots. Low-melting point tetragonal precipitates were found in all Ni-Ti-Cu-Pd alloys. Most frequently observed were semi-coherent, nanometer-sized Pd5Ti3, Cu2Ti, CuTi and Cu-rich CuTiNi/CuTiPd precipitates. Furthermore, small amounts of Ti-oxides were present in all formulations, which act as nucleation sites for macroscopic (several µm), incoherent Ti2Ni and Ti2Cu precipitates with a high melting point above 1100 °C.
- Despite low cooling rates (1–10 °C/min) of furnace cooling after the homogenization treatment, the content of the secondary phases still increased after the solution treatment and aging at 550 °C × 3 h, confirming a metastable state of homogenized VIM cast alloys.
- This metastable state causes significant deviations in the matrix chemistry from the overall composition. A non-proportional amount of the elements will be dissolved in high melting point precipitates and oxides and deteriorate the matrix composition. Another quantity of elements is distributed in semi-coherent precipitates, which form and can be dissolved by applying heat treatments. Therefore, the highly sensitive Co-Factor condition is difficult to match, and the correlation with calculated/measured λ2 and thermal hysteresis in the here-tested alloys was low. New models that predict the change in the matrix composition due to the formation and precipitation of non-shape memory phases needs to be developed and applied to counterbalance the described effect in the design of alloys.
- In VIM cast alloys, the solution treatment with subsequent aging seemed an effective strategy for most formulations to further reduce hysteresis. However, precipitates tend to enrich also at the grain boundaries, which is expected to impact the workability of the alloys. In particular, in the high Pd-containing alloys, where two different types of precipitates were observed at the grain boundaries, the processability could be compromised after low-temperature annealing.
- An apparent correlation between CC II, martensitic morphology and thermal cycling stability was observed. The here-presented results hint at finer martensite features and higher thermal cycling stability when CC II approaches 0. However, these observations need to be further confirmed as the experiments were not designed to principally investigate this hypothesis.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Alloy Group | Code | Nominal Composition in at. % | Co-Factor Calculations | ||||
---|---|---|---|---|---|---|---|
Ti | Ni | Cu | Pd | CCI: |λ2 − 1| | CCII: Twins Type I/II (1E-4) | ||
A | Ti-lean | 49.8 | 27.6 | 14 | 8.6 | ||
DFT | 50 | 27.3 | 14.1 | 8.6 | 0.0002 | 2.4–4.0 | |
A | Ti50 | 50 | 29.1 | 11.5 | 9.4 | ||
DFT | 50 | 28.9 | 11.7 | 9.4 | 0.0004 | 0.2–1.7 | |
A | Ti-rich | 50.2 | 30.9 | 9 | 9.9 | ||
DFT | 50 | 30.5 | 9.4 | 10.2 | 0.0003 | 1.4–2.8 | |
B | 5-Pd | 50.2 | 33.3 | 11.5 | 5 | ||
DFT | 50 | 33.6 | 11.7 | 4.7 | 0.0012 | 3.8–5.0 | |
B | 15-Pd | 50.2 | 23.3 | 11.5 | 15 | ||
DFT | 50 | 23.4 | 11.7 | 14.8 | 0.0009 | 16.6–18.6 | |
B | 20-Pd | 50.2 | 18.3 | 11.5 | 20 | ||
DFT | 50 | 18.0 | 11.7 | 20.3 | 0.0014 | 27.5–29.8 |
Alloy | 900 °C × 24 h (HOMO) (°C) | 900 °C × 30 min (ST) (°C) | 550 °C × 180 min (AGED) (°C) | |||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Furnace Cooled | Water Quenched | Water Quenched | ||||||||||||||||
As | Ap | Af | Ms | Mp | Mf | As | Ap | Af | Ms | Mp | Mf | As | Ap | Af | Ms | Mp | Mf | |
Ti-lean | 16 | 24 | 31 | 20 | 13 | −1 | 23 | 34 | 39 | 21 | 13 | 1 | 21 | 30 | 44 | 23 | 14 | 4 |
Ti50 | 37 | 47 | 58 | 35 | 26 | 12 | 33 | 50 | 57 | 40 | 26 | 11 | 40 | 49 | 57 | 38 | 28 | 14 |
Ti-rich | 44 | 57 | 61 | 53 | 43 | 32 | 50 | 65 | 75 | 52 | 38 | 23 | 51 | 57 | 61 | 52 | 48 | 39 |
Alloy | 900 °C × 24 h (HOMO) (°C) | 900 °C × 30 min (ST) (°C) | 550 °C × 180 min (AGED) (°C) | |||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Furnace Cooled | Water Quenched | Water Quenched | ||||||||||||||||
As | Ap | Af | Ms | Mp | Mf | As | Ap | Af | Ms | Mp | Mf | As | Ap | Af | Ms | Mp | Mf | |
5-Pd | 77 | 85 | 90 | 77 | 70 | 62 | 54 | 71 | 80 | 54 | 40 | 26 | 66 | 76 | 83 | 73 | 64 | 50 |
15-Pd | 56 | 63 | 67 | 56 | 52 | 44 | 74 | 86 | 93 | 75 | 68 | 57 | 56 | 63 | 67 | 56 | 52 | 44 |
20-Pd | 119 | 131 | 135 | 124 | 116 | 103 | 124 | 141 | 151 | 121 | 106 | 89 | 124 | 132 | 136 | 122 | 116 | 107 |
ρ (kg/m3) | K (W/mK) | c (J/kgK) | T (K) | N | A (mm2) |
7600 | 25 | 470 | 298 | 2 | 5452 |
ρm (kg/m3) | L (J/kg) | cm (J/kgK) | Tm (K) | ΔTs (K) | V (mm3) |
6450 | 25,000 | 320 | 1583 | 70 | 62,015 |
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Lemke, J.N.; Gallino, F.; Cresci, M.; Zilio, S.; Coda, A. Low-Hysteresis Shape Memory Alloy Scale-Up: DSC, XRD and Microstructure Analysis on Heat-Treated Vacuum Induction Melted Ni-Ti-Cu-Pd Alloys. Metals 2021, 11, 1387. https://doi.org/10.3390/met11091387
Lemke JN, Gallino F, Cresci M, Zilio S, Coda A. Low-Hysteresis Shape Memory Alloy Scale-Up: DSC, XRD and Microstructure Analysis on Heat-Treated Vacuum Induction Melted Ni-Ti-Cu-Pd Alloys. Metals. 2021; 11(9):1387. https://doi.org/10.3390/met11091387
Chicago/Turabian StyleLemke, Jannis Nicolas, Federico Gallino, Matteo Cresci, Stefano Zilio, and Alberto Coda. 2021. "Low-Hysteresis Shape Memory Alloy Scale-Up: DSC, XRD and Microstructure Analysis on Heat-Treated Vacuum Induction Melted Ni-Ti-Cu-Pd Alloys" Metals 11, no. 9: 1387. https://doi.org/10.3390/met11091387