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Rapid solidification of a FeSi intermetallic compound in undercooled melts: dendrite growth and microstructure transitions

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Abstract

Rapid solidification of a FeSi stoichiometric intermetallic compound was studied using the glass fluxing method. The recalescence process was in situ observed for the first time by the infrared high-speed high-resolution cameras. The dendrite envelope was found to be non-isothermal during the recalescence process. The growth velocity increased first, then decreased and finally held nearly constant. The average dendrite growth velocity for the recalescence process increased monotonically with undercooling and was described well by the dendrite growth model for a stoichiometric intermetallic compound. At low undercooling, the microstructure transition from coarse dendrites to refined grains was consistent with the dendrite fragmentation model and the chemical superheating model. At high undercooling, dendrite deformation triggers stress accumulation upon rapid solidification, thus providing the driving force for recrystallization. However, there were no evidences for annealing twins accompanied by recrystallization as well as random textures due to recrystallization nucleation. From the local misorientation map, the grain refinement mechanism was suggested to be stress-induced dendrite fragmentation. This study is helpful for not only understanding the intrinsic mechanisms of microstructure transitions in theory but also controlling microstructures and performance of intermetallic compounds in practical applications.

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Notes

  1. The transition from dendrite to dendritic seaweed was also reported for rapid solidification of Ni3Ge intermetallic compound processed by drop-tube [33,34,35].

  2. The compound FeSi crystallizes in cubic B20 structure, and the corresponding space group is P213. Each primitive unit cell in the B20 structure contains eight atoms (four Fe atoms and four Si atoms), and any one of the atoms is surrounded by seven nearest neighbor atoms of the opposite element. Both Fe and Si atoms occupy the Wyckoff position of 4a (x, x, x). The coordinates of the position are (u, u, u), (0.5 + u, 0.5 − u, −u), (−u, 0.5 + u, 0.5 − u), (0.5 − u, −u, 0.5 − u), where uFe = 0.173a and uSi = 0.842a with a = 449 pm [38].

  3. This camera is equipped with a refrigerated mercury cadmium telluride detector with the ability to produce a clear thermal image of 640 × 512 pixels and a temperature difference of less than 25 mK.

  4. The second recalescence event is so weak that it cannot be captured by the high-speed cameras.

  5. Because we aim to study grain refinement mechanisms and dendrite growth kinetics of the FeSi intermetallic compound, further identifying the crystal structure of the secondary phase is not shown here.

  6. It should be noted that the thermal undercooling ΔTT adopted here is for an isothermal dendrite under a steady-state condition. The dendrite envelope recorded by the infrared high-speed camera shows that it is under a non-steady-state condition and is a non-isothermal one; see Fig. 4.

  7. \( \Delta t_{\text{pl}} \) is defined in the cooling curves as the time difference between the highest recalescence temperature and the inflection point after recalescence. It should be noted that if the overall solidification is adopted, the cooling history can be predicted, according to which \( \Delta t_{\text{pl}} \) can be obtained theoretically [22]. In this case, dendrite fragmentation in undercooled melts can be described in a self-consistent way.

  8. A plenty of sub-grains were also found within the coarse grains for rapid solidification in an undercooled CoNi equiatomic alloy [55].

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Acknowledgements

This work was done under the Natural Science Foundation of China (No. 51975474), the Science Fund for Distinguished Young Scholars from Shaanxi province (2018-JC007), the Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University (No. CX201907) and the Fundamental Research Funds for the Central Universities. The authors appreciate Dr. Vipul Bhardwaj for reading and polishing the manuscript.

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  1. State Key Laboratory of Solidification Processing, Center of Advanced Lubrication and Seal Materials, Northwestern Polytechnical University, **’an, 710072, Shaanxi, People’s Republic of China

    Jianbao Zhang, Fan Zhang, Xuan Luo, Qing Zhou & Haifeng Wang

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Appendix: Secondary solidification

Appendix: Secondary solidification

In this study, secondary solidification (i.e., eutectic solidification) happens after primary solidification of the FeSi intermetallic compound at undercooling of ΔT = 90 K, ΔT = 147 K, ΔT = 194 K and ΔT = 259 K; see Fig. 1. In a recent study on rapid solidification of a Ni31Si12 intermetallic compound in undercooled melts [36], secondary solidification was found when ΔT > 119 K. It seems that secondary solidification after primary solidification of an intermetallic compound appeared frequently in undercooled melts with a congruent composition.

Here, the kinetic phase diagram is used to illustrate the phase transition as the interface velocity increases. The kinetic phase diagram is the phase diagram for a given growth velocity, which shows the relationship between the interface temperature and compositions at a given growth velocity. For example, for the kinetic phase diagram calculated by Assadi [17], the kinetic congruent melting point of the Ni–Al alloy shifts toward to the Al-rich side. In the Co–Si kinetic phase diagram, the kinetic congruent melting point shifts toward to the Si-rich side with the increasing growth velocity [37].

Generally, the non-equilibrium interface condition has two effects on the kinetic phase diagram. These are shown schematically for a non-stoichiometric Fe–Si intermetallic compound in Fig. 16. First, the kinetic congruent melting point deviates from the equilibrium one due to disorder trap** and kinetic undercooling; see the red solid line in Fig. 16. Second, the solidus and liquidus gradually coincide due to the solute trap** effect; see the non-solid lines in Fig. 16. Therefore, the congruent composition can be within the solid–liquid two-phase zone in the kinetic phase diagrams. After primary rapid solidification of the FeSi intermetallic compound, the remained melt can be solidified into eutectics; see Figs. 7a and 16. The amount of metastable phase within the inter-dendrites can be seen from Fig. 5, which first increases and then decreases with undercooling. The metastable phase completely disappears when the undistributed solidified microstructure occurs at ΔT = 298 K. In other words, when the undercooling is high enough, complete solute trap** takes place, thus resulting in diffusionless solidification. According to the microstructure evolution of the FeSi intermetallic compound, the schematic diagram of the metastable phase formation and disappearance with the growth velocity is shown at the bottom of Fig. 16.

Figure 16
figure 16

Schematic kinetic phase diagrams for a non-stoichiometric FeSi intermetallic compound

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In the previous study of Lai et al. [36], the second phase β2-Ni3Si is a stable phase in the phase diagram. In this study, however, it is an unknown metastable phase. It should be noted that the formation of such a metastable phase is quite different from phase selection due to either thermodynamics [56] or kinetics [10]. For the latter, the mechanism can be nucleation controlled or growth controlled [10]. The result is that the stable phase is replaced by another stable phase or metastable phase. For the undercooled melts with a congruent composition, however, the intermetallic compound is always solidified primarily and the secondary phase is always a minor one.

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Zhang, J., Zhang, F., Luo, X. et al. Rapid solidification of a FeSi intermetallic compound in undercooled melts: dendrite growth and microstructure transitions. J Mater Sci 55, 4094–4112 (2020). https://doi.org/10.1007/s10853-019-04265-2

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