Microstructural characteristics of Ni-Sb eutectic alloys under substantial undercooling and containerless solidification conditions

Both Ni-36 wt pct Sb and Ni-52.8 wt pct Sb eutectic alloys were highly undercooled and rapidly solidified with the glass-fluxing method and drop-tube technique. Bulk samples of Ni-36 pct Sb and Ni-52.8 pct Sb eutectic alloys were undercooled by up to 225 K (0.16 T _E ) and 218 K (0.16 T _E ), respectively, with the glass-fluxing method. A transition from lamellar eutectic to anomalous eutectic was revealed beyond a critical undercooling ΔT ₁*, which was complete at an undercooling of ΔT ₂*. For Ni-36 pct Sb, ΔT ₁*≈60 K and ΔT ₂*≈218 K; for Ni-52.8 pct Sb, ΔT ₁*≈40 K and ΔT ₂*≈139 K. Under a drop-tube containerless solidification condition, the eutectic microstructures of these two eutectic alloys also exhibit such a “lamellar eutectic-anomalous eutectic” morphology transition. Meanwhile, a kind of spherical anomalous eutectic grain was found in a Ni-36 pct Sb eutectic alloy processed by the drop-tube technique, which was ascribed to the good spatial symmetry of the temperature field and concentration field caused by a reduced gravity condition during free fall. During the rapid solidification of a Ni-52.8 pct Sb eutectic alloy, surface nucleation dominates the nucleation event, even when the undercooling is relatively large. Theoretical calculations on the basis of the current eutectic growth and dendritic growth models reveal that γ-Ni₅Sb₂ dendritic growth displaces eutectic growth at large undercoolings in these two eutectic alloys. The tendency of independent nucleation of the two eutectic phases and their cooperative dendrite growth are responsible for the lamellar eutectic-anomalous eutectic microstructural transition.     

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).     

Dendritic Growth of Undercooled Nickel-Tin: Part III

Studies were made of structure and solute distribution in undercooled droplets of nickel-25 wt pct tin alloy and the eutectic nickel-32.5 wt pct tin alloy. Structures of levitation melted droplets of the Ni-25 wt pct Sn alloy showed a gradual and continuous transition from dendritic to fine-grained spherical with increasing initial undercooling up to about 180 K. Results suggest that all samples solidified dendritically and that the final structures obtained were largely the result of ripening. Experimental data on minimum solute composition in the samples produced are bounded by two calculated curves, both of which assume equilibrium at all liquid-solid interfaces during recalescence and subsequent cooling. One assumes complete diffusion in the solid during recalescence; the other assumes limited diffusion, but partial remelting to avoid superheating of the solid. Several observations support the view that the eutectic alloy solidifies dendritically, much as the hypoeutectic alloy does. Surface dendrites were seen in regions of surface shrinkage cavities and a coarse “dendritic” structure can be discerned on polished sections, which seems to correspond to the large surface “dendrites” seen by high-speed photographs of the hypoeutectic alloy. The structure of highly undercooled eutectic samples is composed fully of an anomalous eutectic. Samples solidified with intermediate amounts of undercooling possess some lamellar eutectic which, it is believed, solidified after recalescence was complete.     

Dendritic growth of undercooled nickel-tin: Part II

High-speed optical temperature measurements were made of the solidification behavior of levitated metal samples within a transparent glass medium. Two undercooled Ni-Sn alloys were examined, one a hypoeutectic alloy and the other of eutectic composition. Recalescence times for the 9 mm diameter samples studied decreased with increasing undercooling from the order of 1.0 second at 50 K under-cooling to less than 10⁻³ second for undercoolings greater than 200 K. Both alloys recalesced smoothly to a maximum recalescence temperature at which the solid was at or near its equilibrium composition and equilibrium weight fraction. For the samples of hypoeutectic alloy that recalesced above the eutectic temperature, a second nucleation event occurred on cooling to the eutectic temperature. For samples which recalesced only to the eutectic temperature, no subsequent nucleation event was observed on cooling. It is inferred in this latter case that both the α and β phases were present at the end of recalescence. The thermal data obtained suggest a solidification model involving (1) dendrites of very fine structure growing into the melt at temperatures near the bulk undercooling temperature, (2) thickening of dendrite arms with rapid recalescence, and (3) continued, much slower recalescence accompanying dendrite ripening.     

Determination of Solid Fraction from Cooling Curve

A new method to determine directly the solid fraction using the cooling curve was proposed for solidification of undercooled melts. Then, to construct three different baselines, a sudden function ξ _α (x) is introduced. In terms of the ξ _α (x) function, accordingly, the solid fractions during solidification of Ni-3.3 wt pct B, Al-7 wt pct Si, Al-14 wt pct Cu, and Fe-4.56 wt pct Ni alloys were predicted. The predictions of the primary, the regular lamellar eutectic, the anomalous eutectic, and the peritectic phases from cooling curves of the solidified samples coincide with the results of measurement or the available methods.     

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.     

Nucleation and phase selection in undercooled Fe-Cr-Ni melts: Part II. Containerless solidification experiments

The solidification behavior of undercooled Fe-Cr-Ni melts of different compositions is investigated with respect to the competitive formation of δ-bcc (ferrite) and γ-fcc phase (austenite). Containerless solidification experiments, electromagnetic levitation melting and drop tube experiments of atomized particles, show that δ (bcc) solidification is preferred in the highly undercooled melt even at compositions where δ is metastable. Time-resolved detection of the recalescence events during crystallization at different undercooling levels enable the determination of a critical undercooling for the transition to metastable bcc phase solidifcation in equilibrium fcc-type alloys. Measurements of the growth velocities of stable and metastable phases, as functions of melt undercooling prior to solidification, reveal that phase selection is controlled by nucleation. Phase selection diagrams for solidification processes as functions of alloy composition and melt undercooling are derived from two types of experiments: X-ray phase analysis of quenched samples and in situ observations of the recalescence events of undercooled melts. The experimental results fit well with the theoretical predictions of the metastable phase diagram and the improved nucleation theory presented in an earlier article. In particular, the tendency of metastable δ phase formation in a wide composition range is confirmed.     

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.     

Metastable Phase Formation and Its Transformation in Highly Undercooled Ni75B25 Alloy

Ni₇₅B₂₅ alloy was solidified at various undercooling. The formation and subsequent transformation of metastable Ni₂₃B₆ phase were clearly identified. If undercooling prior to nucleation is less than a critical value of 240 K (240 °C), the alloy solidifies completely into Ni₃B phase. At larger undercooling, metastable Ni₂₃B₆ phase primarily forms in the melt but then is decomposed into α-Ni and Ni₃B through a eutectoid reaction. The decomposition simultaneously triggers the rapid solidification of residual liquid, due to which a second temperature recalescence occurs. The α-Ni/Ni₃B eutectoid is partially remelted if temperature exceeds the eutectic temperature during the second recalescence. Then, residual Ni₃B grows into coarse round grains while the remaining liquid re-solidifies into α-Ni/Ni₃B eutectic structure in the remelted region. In the case that the eutectic temperature is not reached, the eutectoid product with dot α-Ni distributing in Ni₃B matrix is retained in the solidification structure. A longer delay time between the two temperature recalescence events means less residual liquid, lower recalescence temperature and thus depressed remelting. The formation competition between Ni₃B and Ni₂₃B₆ phases in the alloy melt is nucleation controlled. The heterogeneous site in Ni₇₅B₂₅ alloy melt is a better nucleation substrate for Ni₂₃B₆ phase than for Ni₃B phase.

Graphical abstract

     

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.     

An analysis of the microstructure of rapidly solidified Al-8 wt pct Fe powder

Rapidly solidified powders of Al-8 wt pct Fe exhibit four distinct microstructures with increasing particle diameter in the size range of 5 μm to 45 μm: microcellular α-Al; cellular α-Al; a-Al + Al₆Fe eutectic; and Al₃Fe primary intermetallic structure. Small powder particles (~10 μm or less) undercool significantly prior to solidification and typically exhibit a two-zone microcellular-cellular structure in individual powder particles. In the two-zone microstructure, there is a transition from solidification dominated by internal heat flow during recalescence with high growth rates (microcellular) to solidification dominated by external heat flow and slower growth rates (cellular). The origin of the two-zone microstructure from an initially cellular or dendritic structure is interpreted on the basis of growth controlled primarily by solute redistribution. Larger particles experience little or no initial undercooling prior to solidification and do not exhibit the two-zone structure. The larger particles contain cellular, eutectic, or primary intermetallic structures that are consistent with growth rates controlled by heat extraction through the particle surface (external heat flow).     

Nonequilibrium Solidification,Grain Refinements,and Recrystallization of Deeply Undercooled Ni-20 At. Pct Cu Alloys: Effects of Remelting and Stress

Grain refinement phenomena during the microstructural evolution upon nonequilibrium solidification of deeply undercooled Ni-20 at. pct Cu melts were systematically investigated. The dendrite growth in the bulk undercooled melts was captured by a high-speed camera. The first kind of grain refinement occurring in the low undercooling regimes was explained by a current grain refinement model. Besides, for the dendrite melting mechanism, the stress originating from the solidification contraction and thermal strain in the FMZ during rapid solidification could be a main mechanism causing the second kind of grain refinement above the critical undercooling. This internal stress led to the distortion and breakup of the primary dendrites and was semiquantitatively described by a corrected stress accumulation model. It was found that the stress-induced recrystallization could make the primary microstructures refine substantially after recalescence. A new method, i.e., rapidly quenching the deeply undercooled alloy melts before recalescence, was developed in the present work to produce crystalline alloys, which were still in the cold-worked state and, thus, had the driven force for recrystallization.

     

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.     

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.     

Aligned Ni-In eutectics

Directional solidification of two eutectic alloys in the Ni-In system results in aligned microstructures. The eutectic at 26.5 at. pct In solidifies as ribbons and lamellae of nickel-base solid solution in a matrix of ε-Ni₂In. Peritectoid formation of Ni₃In on cooling drastically alters the morphology, but this reaction can be suppressed by quenching. The peritectoid reaction can then be studied by isothermal heat treatments. The eutectic at 46.6 at. pct In solidifies partly as rods of ε-Ni₂In in a matrix of β-NiIn, partly in a lamellar morphology. Both phases transform on cooling, but because little composition change is involved, the effect on eutectic morphology is slight.     

A new analytical approach to predict spacing selection in lamellar and rod eutectic systems

The Jackson and Hunt (JH) theory has been modified to relax the assumption of isothermal solid/liquid interface used in their treatment. Based on the predictions of this modified theory, the traditional definitions of regular and irregular eutectics are revised. For regular eutectics, the new model identifies a range of spacing within the limits defined by the minimum undercooling of the α and β phases. For the irregular Al-Si eutectic system, two different spacing selection mechanisms were identified: (1) for a particular growth rate, a nearly isothermal interface can be achieved at a unique minimum spacing λ _I ; (2) the average spacing (λ _av >λ _I ) is essentially dictated by the undercooling of the faceted phase. Based on the modified theoretical model, a semiempirical expression has been developed to account for the influence of the temperature gradient, which is dominant in the irregular Al-Si system. The behavior of the Fe-Fe₃C eutectic is also discussed. The theoretical calculations have been found to be in good agreement with the published experimental measurements.     

Containerless processing and rapid solidification of Nb-Si alloys in the niobium-rich eutectic range

Containerless processing and rapid solidification techniques were used to process Nb-Si alloys in the Nb-rich eutectic range. Electromagnetic ally levitated drops were melted and subsequently splat quenched from different temperatures. A variety of eutectic morphologies was obtained as a function of the degree of superheating or undercooling of the drops prior to splatting. Metallic glass was observed only in drops quenched from above the melting temperature. Micro-structures of splats deeply undercooled prior to quenching were very fine and uniform. These results are discussed in terms of classic nucleation theory concepts and the expected heat evolution at different regions of the splat during the rapid quenching process. The locations of the coupled-zone boundaries for the α-Nb + Nb₃Si eutectic are also suggested. Formerly Graduate Student, Vanderbilt University.     

Undercooling-Induced macrosegregation in directional solidification

The accepted primary mechanism for causing macrosegregation in directional solidification (DS) is thermal and solutal convection in the liquid. This article demonstrates the effects of under-cooling and nucleation on macrosegregation and shows that undercooling, in some cases, can be the cause of end-to-end macrosegregation. Alloy ingots of Pb-Sn were directionally solidified upward and downward, with and without undercooling. A thermal gradient of about 5.1 K/cm and a cooling rate of 7.7 K/h were used. Crucibles of borosilicate glass, stainless steel with Cu bottoms, and fused silica were used. High undercoolings were achieved in the glass crucibles, and very low undercoolings were achieved in the steel/Cu crucible. During under-cooling, large, coarse Pb dendrites were found to be present. Large amounts of macrosegregation developed in the undercooled eutectic and hypoeutectic alloys. This segre-gation was found to be due to the nucleation and growth of primary Pb-rich dendrites, continued coarsening of Pb dendrites during undercooling of the interdendritic liquid, Sn enrichment of the liquid, and dendritic fragmentation and settling during and after recalescence. Eutectic ingots that solidified with no undercooling had no macrosegregation, because both Pb and Sn phases were effectively nucleated at the start of solidification, thus initiating the growth of solid of eutectic composition. It is thus shown that undercooling and single-phase nucleation can cause significant macrosegregation by increasing the amount of solute rejected into the liquid and by the movement of unattached dendrites and dendrite fragments, and that macrosegregation in excess of what would be expected due to diffusion transport is not necessarily caused by convection in the liquid.     

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