Phase Selection and Microstructure Evolution in Nonequilibrium Solidification of Fe40Ni40B20 Alloy

Phase selection and microstructure evolution in nonequilibrium solidification of ternary eutectic Fe₄₀Ni₄₀B₂₀ alloy have been studied. It is shown that γ-(Fe, Ni) and (Fe, Ni)₃B prevail in all the as-solidified samples. No metastable phase has been found in the deeply undercooled samples. This is explained as resulting from the size effect of undercooled solidification. At small and medium undercoolings, the dendrite γ-(Fe, Ni) appears as the leading phase. This is ascribed to the existence of the skewed coupled growth zone in FeNiB alloy. With increasing undercooling, the amount of dendrites first increases and then decreases, accompanied by a transition from regular eutectic to anomalous eutectic. The formation mechanisms of the anomalous eutectics are discussed. Two kinds of microstructure refinement are found with increasing undercooling in a natural or water cooling condition. However, for melts with the same undercooling, the as-solidified microstructure refines first, and then coarsens with an increasing cooling rate. The experimental results show that the nanostructure eutectic cell has been obtained in the case of Ga-In alloy bath cooling with an initial melt undercooling of approximately 50 K (50 °C).     

Controlled undercooling of liquid iron in contact with Al2O3 substrates under varying oxygen partial pressures

The objective of this study was to determine the conditions under which alumina can act as a heterogeneous nucleant to initiate the solidification of undercooled liquid iron. The undercooling of a pure iron sessile droplet in contact with Al₂O₃ substrates was measured under controlled oxygen partial pressures by observing droplet recalescence. The experimental results indicated that the undercooling of liquid iron, in contact with an Al₂O₃ substrate, did not have a unique value, varied from 0 °C to 290 °C, and was significantly affected by the oxygen content of the gas phase and the degree of interaction between the oxide and the metal. Deep undercoolings are possible at low oxygen potentials, provided the oxygen potential is such that substantial substrate decomposition does not occur. The measured undercooling was a strong function of gas phase oxygen content and a maximum in undercooling of 290 °C was measured at PO₂=10⁻¹⁹ atm. The variation in undercooling was related to the wetting of the substrate by the liquid metal, where the deepest undercoolings occurred when the highest contact angle between the substrate and the liquid droplet was achieved.     

Nucleation Catalysis in Aluminum Alloy A356 Using Nanoscale Inoculants

Different types of nanoparticles in aluminum (Al) alloy A356 nanocomposites were shown to catalyze nucleation of the primary Al phase. Nanoparticles of SiC β, TiC, Al₂O₃ α, and Al₂O₃ γ were added to and dispersed in the A356 matrix as nucleation catalysts using an ultrasonic mixing technique. Using the droplet emulsion technique (DET), undercoolings in the nanocomposites were shown to be significantly reduced compared to the reference A356. None of the nanocomposites had a population of highly undercooled droplets that were observed in the reference samples. Also, with the exception of the A356/Al₂O₃ α nanocomposite, all nanocomposites showed a reduction in undercooling necessary for the onset of primary Al nucleation. The observed nanocomposite undercoolings generally agreed with the undercooling necessary for free growth. The atomic structure of the particles showed an influence on nucleation potency as A356/Al₂O₃ γ nanocomposites had smaller undercoolings than A356/Al₂O₃ α nanocomposites. The nucleation catalysis illustrates the feasibility of, and basis for, grain refinement in metal matrix nanocomposites (MMNCs).     

Crystal-Growth Transition and Homogenous Nucleation Undercooling of Bismuth

The cross-sectional and surface morphologies of highly undercooled bismuth samples are investigated by optical microscopy and scanning electron microscopy. It is found that the grain morphology can be classified into three types. When the undercooling is less than 49 K (49 °C), flaky grains with pronounced edges and faces are arranged parallel to each other, showing the feature of lateral growth. When the undercooling is over 95 K (95 °C), refined equiaxial grains with several smooth bulges on the surface of each grain are randomly arranged, showing the feature of continuous growth. In the undercooling region from 49 K to 95 K (49 °C to 95 °C), the features of both lateral and continuous growth are observed. The microstructures within the sample grains obtained at different undercooling regions are dissimilar, but they all show features of anisotropic growth. Based on the critical growth-transition undercoolings, direct expressions that express the relationship between the solid-liquid interface energy and temperature are determined. Homogenous nucleation undercooling is also predicted according to the solid-liquid interface energy obtained from the critical growth-transition undercooling. The predicted results of homogenous nucleation undercooling for bismuth are in good agreement with the experimental results.     

Effect of the primary phase on grain coarsening in undercooled Fe-Co alloys

Fe-Co alloy melts with Co contents of 10, 30, and 60 at. pct were undercooled to investigate the dependence of the primary phase on grain coarsening. A pronounced characteristic is that the metastable fcc phase in the Fe-10 at. pct Co alloy and the metastable bcc phase in the Fe-30 at. pct Co alloy will primarily nucleate when undercoolings of the melts are larger than the critical undercoolings for the formation of metastable phases in both alloys. No metastable bcc phase can be observed in the Fe-60 at. pct Co alloy, even when solidified at the maximum undercooling of ΔT = 312 K. Microstructural investigation shows that the grain size in Fe-10 and Fe-30 at. pct Co alloys increases with undercoolings when the undercoolings of the melts exceed the critical undercoolings. The grain size of the Fe-60 at. pct Co alloy solidified in the undercooling range of 30 to 312 K, in which no metastable phase can be produced, is much finer than those of the Fe-10 and Fe-30 at. pct Co alloys after the formation of metastable phases. The model for breakage of the primary metastable dendrite at the solid-liquid interface during recalescence and remelting of dendrite cores is suggested on the basis of microstructures observed in the Fe-10 and Fe-30 at. pct Co alloys. The grain coarsening after the formation of metastable phases is analyzed, indicating that the different crystal structures present after the crystallization of the primary phase may play a significant role in determining the final grain size in the undercooled Fe-Co melts.     

Denucleation

Ultrarapid cooling may result in material with extremely fine grain size and interdendritic spacing, or containing supersaturated solutions or nonequilibrium phases. Unfortunately, ultrarapid cooling cannot be obtained in large masses of metal; thus the interesting properties cannot be exploited commercially. The same structures can be obtained by denucleation, that is removal or neutralization of the nucleants that act at low undercooling. A denucleated melt, regardless of its size, can be undercooled to a temperature well below its freezing point, where it can be made to freeze rapidly on a chosen nucleant. Electro-lytically refined aluminum crystallizes normally with a fairly coarse grain at 1 to 2°C undercooling. By removing all nucleants with less than 5°C undercooling a grain size of less than 1 mm diam was achieved in a furnace cooled sample. In aluminum-manganese alloys, denucleation produces refinement of the grain structure in continuously cast billets and retention in solution of a higher percentage of manganese, in pure aluminum columnar grain and crystallization twins are found in plaster molds. By denucleation of aluminum-iron alloys, the FeAl₆ phase can be made to appear in samples cooled at commercial rates of a few °C/sec and eutectic structures can be obtained in alloys with 4 pct Fe. In cast iron removal of nucleants with low undercooling shifts the crystallization from primary graphite to primary austenite. Formerly Metallurgist, Revere Copper and Brass Incorporated     

Dendrite growth processes of silicon and germanium from highly undercooled melts

The crystal growth behavior of a semiconductor from a very highly undercooled melt is expected to be different from that of a metal. In the present experiment, highly pure undoped Si and Ge were undercooled by an electromagnetic levitation method, and their crystal growth velocities (V) were measured as a function of undercooling (ΔT). The value of V increased with ΔT, and V=26 m/s was observed at ΔT=260 K for Si. This result corresponds well with the predicted value based on the dendrite growth theory. The growth behaviors of Si and Ge were found to be thermally controlled in the measured range of undercooling. The microstructures of samples solidified from undercooled liquid were investigated, and the amount of dendrites immediately after recalescence increased with undercooling. The dendrite growth was also observed by a high-speed camera.     

Effects of Undercooling and Cooling Rate on Peritectic Phase Crystallization Within Ni-Zr Alloy Melt

The liquid Ni-16.75 at. pct Zr peritectic alloy was substantially undercooled and containerlessly solidified by an electromagnetic levitator and a drop tube. The dependence of the peritectic solidification mode on undercooling was established based on the results of the solidified microstructures, crystal growth velocity, as well as X-ray diffraction patterns. Below a critical undercooling of 124 K, the primary Ni₇Zr₂ phase preferentially nucleates and grows from the undercooled liquid, which is followed by a peritectic reaction of Ni₇Zr₂+L → Ni₅Zr. The corresponding microstructure is composed of the Ni₇Zr₂ dendrites, peritectic Ni₅Zr phase, and inter-dendritic eutectic. Nevertheless, once the liquid undercooling exceeds the critical undercooling, the peritectic Ni₅Zr phase directly precipitates from this undercooled liquid. However, a negligible amount of residual Ni₇Zr₂ phase still appears in the microstructure, indicating that nucleation and growth of the Ni₇Zr₂ phase are not completely suppressed. The micromechanical property of the peritectic Ni₅Zr phase in terms of the Vickers microhardness is enhanced, which is ascribed to the transition of the peritectic solidification mode. To suppress the formation of the primary phase completely, this alloy was also containerlessly solidified in free fall experiments. Typical peritectic solidified microstructure forms in large droplets, while only the peritectic Ni₅Zr phase appears in smaller droplets, which gives an indication that the peritectic Ni₅Zr phase directly precipitates from the undercooled liquid by completely suppressing the growth of the primary Ni₇Zr₂ phase and the peritectic reaction due to the combined effects of the large undercooling and high cooling rate.     

Solidification of highly undercooled Sn- Pb alloy droplets

Experimental work is described on undercooling and structure of tin-lead droplets emulsified in oil. The droplets, predominantly in the size range of 10 to 20 μm, were cooled at rates (just before nucleation) ranging from about 10^-1 K per second to 10⁶ K per second. The higher cooling rates were obtained by a newly developed technique of quenching the emulsified droplets in a cold liquid. Measured undercoolings (at the lower cooling rates) ranged up to about 100 K. Structures obtained depend strongly on undercooling, cooling rate before and after nucleation, and alloy composition. Droplets containing up to 5 wt pct Pb were apparently single phase when undercooled and rapidly quenched. Droplets in the composition range of about 25 wt pct to 90 wt pct Pb solidified dendritically, even at the most rapid quench rates employed, apparently because these alloys undercooled only slightly before nucleation of the primary phase. Formerly Graduate Research Assistant and Postdoctoral Associate in the Department of Materials Science and Engineering, Massachusetts Institute of Technology.     

Containerless solidification of highly undercooled mullite melts: Crystal growth behavior and microstructure formation

A mullite (3Al₂O₃·2SiO₂) sample has been levitated and undercooled in an aero-acoustic levitator, so as to investigate the solidification behavior in a containerless condition. Crystal-growth velocities are measured as a function of melt undercoolings, which increase slowly with melt undercoolings up to 380 K and then increase quickly when undercoolings exceed 400 K. In order to elucidate the crystal growth and solidification behavior, the relationship of melt viscosities as a function of melt undercoolings is established on the basis of the fact that molten mullite melts are fragile, from which the atomic diffusivity is calculated via the Einstein-Stokes equation. The interface kinetics is analyzed when considering atomic diffusivities. The crystal-growth velocity vs melt undercooling is calculated based on the classical rate theory. Interestingly, two different microstructures are observed; one exhibits a straight, faceted rod without any branching with melt undercoolings up to 400 K, and the other is a feathery faceted dendrite when undercoolings exceed 400 K. The formation of these morphologies is discussed, taking into account the contributions of constitutional and kinetic undercoolings at different bulk undercoolings.     

Microstructural evolution and thermal stability

High-pressure inert gas atomization (HPGA) has been used to produce rapidly solidified Cu-21Nb-2Mo (weight percent) powders with a range of particle sizes and microstructures. The associated microstructures depend on particle size. Specifically, fine-scale particles (\s15 μm@#@) are characterized by a predominance of multiphase spheroids and a small population of Nb-based dendrites in an almost pure matrix of Cu. In contrast, large particles (45 to 75 μm@#@) contain only Nb-based dendrites in a Cu matrix. The volume fraction of the dispersed constituent is much higher in the former instance than in the latter. The change in microstructure with particle size is analyzed in terms of both the amount of undercooling and cooling rate of the liquid droplets prior to and during solidification. In particular, the large undercoolings in the fine particles are believed to induce a nonequilibrium liquid phase separation which results in a high volume fraction of spheroidal, multiphase Nb-Cu particles within a Cu-rich matrix containing Nb-rich dendrites. High-temperature (900 °C) isothermal annealing treatments have also been performed on consolidated material to determine the inherent thermal stability of these microstructures.     

Solidification of undercooled dilute tin-lead alloys

The rate of solidification of dilute tin-lead alloys has been measured as a function of the initial undercooling (up to 45°C) and the solute content (up to 2 wt pct lead). Solidified specimens were examined by metallography and X-ray diffraction to obtain information on the solidification process and the resulting grain structure. Over an intermediate range of undercoolings, it was found that dendrites grow in the tin-lead alloys as much as four times faster than in pure tin at the same undercooling. This result is inconsistent with any present theories for dendrite growth kinetics in binary alloys. At both lower and higher undercoolings there is no evidence for growth by simple extension of dendrites along the specimen, and solidification rate measurements made under these conditions are probably not indicative of normal dendrite growth kinetics. A. W. Urquhart and G. L. F. Powell were formerly at the Thayer School of Engineering.     

The velocity of solidification of highly undercooled nickel

At large undercoolings (τ;10 pctT _M, present theories relating solidification velocity to degree of undercooling do not agree well with reported experimental data for the solidification velocity of nickel as a function of undercooling. The present work shows that this discrepancy is due to two factors. First, the majority of previously reported results overestimate the solidification velocity of nickel at large undercoolings. Second, the scatter in experimental data is so large that a functional relationship between undercooling and velocity is not evident. In this study, the solidification velocity of undercooled nickel was measured using a linear array of 38 photodiodes. The results indicate that the velocity of the thermal field generated by the solid/liquid interface approaches a maximum velocity of 20 m s⁻¹ atΔT} ≈ 10 pctT _M (173 K) and men remains constant with increasing undercooling. This suggests that the velocity of the solid/liquid interface, at undercoolings greater than 10 pctT _M, could be limited by attachment kinetics at the interface. GABRIEL CARRO, formerly Research Associate, Department of Applied and Engineering Sciences, Vanderbilt University     

Direct observation of the crystal-growth transition in undercooled silicon

Using an electromagnetic levitation facility with a laser heating unit, silicon droplets were highly undercooled in the containerless state. The crystal morphologies on the surface of the undercooled droplets during the solidification process and after solidification were recorded live by using a high-speed camera and were observed by scanning electron microscopy. The growth behavior of silicon was found to vary not only with the nucleation undercooling, but also with the time after nucleation. In the earlier stage of solidification, the silicon grew in lateral, intermediary, and continuous modes at low, medium, and high undercoolings, respectively. In the later stage of solidification, the growth of highly undercooled silicon can transform to the lateral mode from the nonlateral one. The transition time of the sample with 320 K of undercooling was about 535 ms after recalescence, which was much later than the time where recalescence was completed.     

Dendritic growth of undercooled nickel-tin: Part I

Solidification of undercooled Ni-25 wt pct Sn alloy was observed by high-speed cinematography and results compared with optical temperature measurements. Samples studied were rectangular in cross-section, and were encased in glass. Cinematographic measurements were carried out on samples undercooled from 68 to 146 K. These undercoolings compare with a temperature range of 199 K from the equilibrium liquidus to the extrapolated equilibrium solidus. At all undercoolings studied, the high-speed photography revealed that solidification during the period of recalescence took place with a dendrite-like front moving across the sample surface. Spacings of the apparent “dendrite” were on the order of millimeters. The growth front moved at measured velocities ranging from 0.07 meters per second at 68 K undercooling to 0.74 meters per second at 146 K undercooling. These velocities agree well with results of calculations according to the model for dendrite growth of Lipton, Kurz, and Trivedi. It is concluded that the coarse structure observed comprises an array of very much finer, solute-controlled dendrites.     

Microstructure of Y3Al5O12 garnet solidified from the melt undercooled beyond the hypercooling limit

The microstructural evolution of Y₃Al₅O₁₂ garnet (YAG) in a wide undercooling range beyond the hypercooling limit (ΔT _hyp) was investigated by containerless solidification processing. The dendrite to cellular-dendrite transition at high-growth velocity was observed at the undercooling beyond ΔT _hyp. This transition may be explained by the hypothesis that it is difficult to form the well-developed secondary-dendritic arms from the hypercooled melt because of no remaining melt in the interdendritic regions. With a further increase in undercooling beyond ΔT _hyp, a cellular microstructure disappeared, and copious amounts of small particles appeared at an undercooling of approximately 1000 K, which is near the glass-transition temperature where the viscosity is approximately 10¹² Pas. It is suggested that multiple nucleation occurred in the highly viscous undercooled melt because of the high nucleation rate. The grain size of YAG, which was analyzed as a function of undercooling, gradually decreased with increasing undercooling even beyond ΔT _hyp, and no fragmentation of dendrites was observed.     

Phase Selection in Undercooled Ni-3.3 Wt Pct B Alloy Melt

The change of eutectic solidification mode in undercooled Ni-3.3 wt pct B melt was studied by fluxing and cyclic superheating. The eutectic structure is mainly controlled by the undercooling for eutectic solidification, ΔT ₂, instead of ΔT ₁, the undercooling for primary solidification. At a small ?T ₂ [e.g., 56 K (56 °C)], the stable eutectic reaction (L → Ni₃B + Ni) occurs and the eutectic morphology consists of lamellar and anomalous eutectic; whereas at a larger ?T ₂ [≥140 K (140 °C)], the metastable eutectic reaction (L → Ni₂₃B₆ + Ni) occurs and the eutectic morphology consists of matrix, network boundary, and two kinds of dot phases. Further analysis declares that the regularly distributed dot phases with larger size come from the metastable eutectic transformation and are identified as α-Ni structure, whereas the irregularly distributed ones with smaller size are a product of the metastable decomposition and tend to have a similar structure to α-Ni as it grows. Calculation of the classical nucleation theory shows that the competitive nucleation between Ni₂₃B₆ and Ni₃B leads to a critical undercooling, ΔT ₂ ^* [125 K < ΔT ₂ ^* < 157 K (125 °C < ?T ₂ ^* < 157 °C)], for the metastable/stable eutectic formation.     

Phase selection in undercooled ti3sn melts

The solidification of undercooled Ti₃Sn melts was investigated using electromagnetic levitation and electrohydrodynamic atomization experiments followed by extensive microstructural char- acterization. The study was motivated by several reports on the kinetic preference for the body- centered cubic (bcc) phase over more closely packed disordered and ordered structures during competitive crystallization from undercooled melts. At low undercoolings, Ti₃Sn melts yield the equilibrium ordered hexagonal DO₁₉ structure, which is retained without change upon cool- ing. Undercoolings between ~100 and ~300 K yield primary dendrites with hexagonal sym- metry but a final microstructure which is clearly martensitic in origin. Two previously unknown metastable forms of Ti₃Sn were identified: an ordered base-centered orthorhombic derived from the α martensite and an ordered monoclinic phase related to the face-centered orthorhombic martensite observed in the Ti-V system. Both phases are believed to evolve from the solid state transformation of a high temperature β phase, but the dendritic structure clearly indicates the formation of a hexagonal phase different from DO₁₉,i.e., α. The latter forms in preference to β, which has a larger driving force in at least part of the undercooling regime studied. It is proposed that the primary α transforms to β as a consequence of recalescence, which subse- quently transforms martensitically and orders to yield the observed metastable forms of Ti₃Sn.