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.     

Undercooling and solidification of Al-50 at. pct Si Alloy by electromagnetic levitation

Electromagnetic levitation is applied to achieve containerless solidification of 10-mm-diameter droplets of Al-50 at. pct Si. A maximum undercooling of 320 K is obtained. Phase morphologies on the droplet surfaces and on the deeply etched sections of the samples solidified at different undercoolings are examined by scanning electron microscopy. The primary silicon shows well-developed faceted dendrites at a small undercooling, but a fine granular form at a large undercooling. Stratified deposits of aluminum are found within the primary silicon plates, arising from solute pileup during growth. The microstructural refinement at a large undercooling has its origins in solute restriction of crystal growth and in fragmentation of the primary silicon dendrites. The form of the Al-Si eutectic is also found to be changed into an anomalous form at a large undercooling.     

Experimental and Modeling Studies of the Lamellar Eutectic Growth of Mg-Al Alloy

Directionally solidified samples of Mg-32.3 wt pct Al eutectic alloy were produced under an argon atmosphere in a vacuum Bridgman-type furnace to study the eutectic growth with different growth velocities. Typical features such as steady-state lamellar eutectic growth, lamellar branching at the quenching interface, and the formation of colony structures due to the impurity of the Mg-Al binary alloy were observed using a JEOL 6301F scanning electron microscope (JEOL Ltd., Tokyo, Japan). The lamellar spacing of the two eutectic phases was measured on the transverse sections of the samples. It was found that the relationship between the measured lamellar spacing and growth velocity agreed well with the prediction of the Jackson-Hunt model. Subsequent studies of Mg-Al eutectic growth were conducted using a numerical model based on the cellular automaton (CA) method. Taking account of the solute diffusion, constitutional undercooling, and curvature undercooling, modeling of steady-state lamellar eutectic growth was achieved. A systematic investigation of the eutectic growth morphology and lamellar spacing of the Mg-Al eutectic was carried out under directional solidification with different undercoolings, initial lamellar spacings, temperature gradients, and growth velocities. The results showed that under the interaction between solute diffusion and surface energy, the adjustment of eutectic lamellar spacing was accomplished by nucleation, lamellar branching, lamellar termination, and overgrowth. The simulated results were consistent with both the experimental results and the Jackson-Hunt eutectic theory.     

Microstructure and mechanical properties of unidirectionally solidified Al-Si-Ni ternary eutectic

Al-10.98 pct Si-4.9 pct Ni ternary eutectic alloy was unidirectionally solidified at growth rates from 1.39μm/sec to 6.95μm/sec. Binary Al-Ni and Al-Si eutectics prepared from the same purity metals were also solidified under similar conditions to characterize the growth conditions under the conditions of present study. NiAl₃ phase appeared as fibers in the binary Al-Ni eutectic and silicon appeared as irregular plates in the binary Al-Si eutectic. However, in the ternary Al-Si-Ni eutectic alloy both NiAl₃ and silicon phases appeared as irregular plates dispersed in α-Al phase, without any regular repctitive arrangement. The size and spacing of NiAl₃ and Si platelets in cone shaped colonies decreased with an increase in the growth rate of the ternary eutectic. Examination of specimen quenched during unidirectional solidification indicated that the ternary eutectic grows with a non-planar interface with both Si and NiAl₃ phases protruding into the liquid. It is concluded that it will be difficult to grow regular ternary eutectic structures even if only one phase has a high entropy of melting. The tensile strength and modulus of unidirectionally solidified Al-Si-Ni eutectic was lower than the chill cast alloys of the same composition, and decreased with a decrease in growth rate. Tensile modulus and strength of ternary Al-Si-Ni eutectic alloys was greater than binary Al-Si eutectic alloy under similar growth conditions, both in the chill cast and in unidirectionally solidified conditions.     

Microstructure and mechanical properties of unidirectionally solidified Al-Si-Ni ternary eutectic

Al-10.98 pct Si-4.9 pct Ni ternary eutectic alloy was unidirectionally solidified at growth rates from 1.39μm/sec to 6.95μm/sec. Binary Al-Ni and Al-Si eutectics prepared from the same purity metals were also solidified under similar conditions to characterize the growth conditions under the conditions of present study. NiAl₃ phase appeared as fibers in the binary Al-Ni eutectic and silicon appeared as irregular plates in the binary Al-Si eutectic. However, in the ternary Al-Si-Ni eutectic alloy both NiAl₃ and silicon phases appeared as irregular plates dispersed in α-Al phase, without any regular repctitive arrangement. The size and spacing of NiAl₃ and Si platelets in cone shaped colonies decreased with an increase in the growth rate of the ternary eutectic. Examination of specimen quenched during unidirectional solidification indicated that the ternary eutectic grows with a non-planar interface with both Si and NiAl₃ phases protruding into the liquid. It is concluded that it will be difficult to grow regular ternary eutectic structures even if only one phase has a high entropy of melting. The tensile strength and modulus of unidirectionally solidified Al-Si-Ni eutectic was lower than the chill cast alloys of the same composition, and decreased with a decrease in growth rate. Tensile modulus and strength of ternary Al-Si-Ni eutectic alloys was greater than binary Al-Si eutectic alloy under similar growth conditions, both in the chill cast and in unidirectionally solidified conditions.     

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.     

Nonequilibrium Solidification Behavior of Co-Si Alloys Near the First Eutectic Point

Adopting a fluxing purification and cyclic superheating technique, Co-10 wt pct Si and Co-15 wt pct Si alloys had been undercooled to realize rapid solidification in this work. It was investigated that the solidification modes and microstructures of Co-Si alloys were deeply influenced by the undercooling of the melts. Both alloys solidified with a near-equilibrium mode in a low undercooling range; the peritectic reaction occurred between the primary phase and the remnant liquids, and it was followed by the eutectic reaction and eutectoid transformation. With the increase of undercooling, both alloys solidified with a nonequilibrium mode, and the peritectic reaction was restrained. As was analyzed, a metastable Co₃Si phase was found in Co-10 wt pct Si alloy when a critical undercooling was achieved.     

Effect of undercooling on the microstructure of Ni-35 at. pct Mo (eutectic) and Ni-38 at. pct Mo (hypereutectic) alloys

Ni-35 at. pct Mo (eutectic) and Ni-38 at. pct Mo (hypereutectic) alloy specimens have been solidified from various levels of undercooling in the differential thermal analysis (DTA) and the electromagnetic levitation (EML) units in a pyrex/vycor bed. The evolution of the microstructure in the solidified specimens has been examined in terms of the degree of undercooling, the nature of the first phase to nucleate from the melt, and the specimen cooling rate. The melt has been observed to undercool more in the presence of intermetallic NiMo (β) phase as compared to that in the presence of nickel-rich solid solution (γ). The “anomalous eutectic” type of microstructure has been shown to result from the initial formation of the dendritic skeleton of either of the two phases, its segmentation due to convection and ripening, and the subsequent nucleation of the other phase in the interdendritic liquid regions. The recalescence behavior has been examined as a function of undercooling and the nature of the phase nucleating first in the melt.     

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.     

Solidification of undercooled Fe-Cr-Ni alloys: Part II. Microstructural evolution

Results are reported on microstructures of Fe-Cr-Ni alloys, solidified over a range of undercoolings and quenched during or after recalescence. Alloys studied contained 70 wt pct Fe and with Cr varying from approximately 15 to 20 wt pct. The three lower Cr alloys were hypoeutectic (with fee as primary phase in equilibrium solidification); the two higher Cr alloys were hypereutectic (with bcc as primary phase in equilibrium solidification). Results obtained are in agreement with predictions based on thermal analyses previously presented; they confirm and extend the understanding gained in that work. The primary phase to solidify in the hypoeutectic alloys is bec when undercooling is greater than an amount which decreases with increasing Cr content. At the lower Cr contents, the stable fcc phase then forms by solid-state transformation of the metastable phase and its subsequent engulfment by additional fcc. At the higher Cr content, transformation is by a peritectic-like reaction in the semisolid state, except near the surface at higher undercoolings where the transformation is massive. In the hypereutectic alloys, primary solidification at all undercoolings is the stable bcc phase. Partial transformation to fcc occurs in the semisolid or solid state, depending on composition and undercooling. Formerly Graduate Student, Department of Materials Science and Engineering, Massachusetts Institute of Technology     

Mechanical behavior of cast single phase alloys solidified from undercooled melts

Several ingots (0.0254 m in diam × 0.10 m long) of nickel-30 wt pct copper, nickel-10 wt pct cobalt and iron-25 wt pct nickel were solidified with various undercoolings up to about 200 K, prior to nucleation of the solid. The materials were mechanically tested in the ascast condition. In nickel-30 wt pct copper and iron-25 wt pct nickel alloys the 0.2 pct offset yield strength, ductility and fatigue strength increased with undercooling. A linear relationship was established between 0.2 pct offset yield strength and the square root of secondary dendrite arm spacing in dendritic alloys (undercooled less than 170 K) or that of grain diameter in nondendritic alloys (undercooled more than 170 K). In iron-25 wt pct nickel limited testing indicated improvements in Charpy V-notch impact strength and in fracture toughness with undercooling. No improvement of tensile properties with undercooling was observed in nickel-10 wt pct cobalt, an alloy which solidified normally with very low microsegregation.     

An Fe-Cr-Nb pseudobinary eutectic alloy

A study has been made of the microstructure and some high temperature mechanical properties of a unidirectionally solidified, pseudobinary Fe-Cr-Nb eutectic alloy. The alloy consists of 22 volume pct of an intermetallic phase in an iron-chromium solid solution matrix. At all solidification rates investigated the eutectic solidified with a cellular solid/liquid interface. The minor phase adopted a fibrous growth morphology except at cell boundaries where it had a plate-like morphology. The system was found to be resistant to microstructural changes at temperatures of up to 1100°C. Fiber reinforcement however was not observed; the strength of the alloy at elevated temperatures was mainly governed by the properties of the matrix phase. Formerly Research Officer, BHP Melbourne Research Laboratories, Melbourne, Victoria, Australia     

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.     

Phase selection during crystallization of undercooled liquid eutectic lead-tin alloys

During rapid solidification substantial amounts of undercooling are in general required for formation of metastable phases. Crystallization at varying levels of undercooling and melting of metastable phases were studied during slow cooling and heating of emulsified PbSn alloys. Besides the experimental demonstration of the reversibility of metastable phase equilibria, two different principal solidification paths have been identified and compared with the established metastable phase diagram and predictions from classical nucleation theory. The results suggest that the most probable solidification path is described by the “step rule” resulting in the formation of metastable phases at low undercooling, whereas the stable eutectic phase mixture crystallizes without metastable phase formation at high undercooling.     

Interactions between iron, manganese, and the Al-Si eutectic in hypoeutectic Al-Si alloys

Sand-cast plates were used to determine the effect of iron and manganese concentrations on porosity levels in Al-9 pct Si-0.5 pct Mg alloys. Iron increased porosity levels. Manganese additions increased porosity levels in alloys with 0.1 pct Fe, but reduced porosity in alloys with 0.6 and 1 pct Fe. Thermal analysis and quenching were undertaken to determine the effect of iron and managanese on the solidification of the Al-Si eutectic. At high iron levels, the presence of large β-Al₅FeSi was found to reduce the number of eutectic nucleation events and increase the eutectic grain size. The preferential formation of α-Al₁₅Mn₃Si₂ upon addition of manganese reversed these effects. It is proposed that this interaction is due to β-Al₅FeSi and the Al-Si eutectic having common nuclei. Porosity levels are proposed to be controlled by the eutectic grain size and the size of the iron-bearing intermetallic particles rather than the specific intermetallic phase that forms.     

Theory of eutectic growth under rapid solidification conditions

The Jackson-Hunt model of eutectic growth at small undercoolings is extended to large undercooling values which are commonly encountered under rapid solidification conditions. The parameters, λ²V and λΔT, are found to deviate from constant values at high velocities, and these deviations depend upon the nature of the metastable phase diagram below the eutectic temperature. A limiting velocity is predicted for the formation of a regular, coupled eutectic structure, and the reason for this limiting velocity is shown to be either the temperature dependent diffusion coefficient or the limit of undercooling.     

Variations of Microsegregation and Second Phase Fraction of Binary Mg-Al Alloys with Solidification Parameters

A systematic experimental investigation on microsegregation and second phase fraction of Mg-Al binary alloys (3, 6, and 9 wt pct Al) has been carried out over a wide range of cooling rates (0.05 to 700 K/s) by employing various casting techniques. In order to explain the experimental results, a solidification model that takes into account dendrite tip undercooling, eutectic undercooling, solute back diffusion, and secondary dendrite arm coarsening was also developed in dynamic linkage with an accurate thermodynamic database. From the experimental data and solidification model, it was found that the second phase fraction in the solidified microstructure is not determined only by cooling rate but varied independently with thermal gradient and solidification velocity. Lastly, the second phase fraction maps for Mg-Al alloys were calculated from the solidification model.     

Modeling of irregular eutectic microstructures in solidification of Al-Si alloys

A modified cellular automaton (MCA) model was developed and applied to simulate the evolution of solidification microstructures of both eutectic and hypoeutectic Al-Si alloys. The present MCA model considers the equilibrium and metastable equilibrium solidification processes in a multiphase system. It accounts for the aspects including the nucleation of a new phase, the growth of primary α dendrites and two eutectic solid phases from a single liquid phase, as well as the coupling between the phase transformation and solute redistribution in liquid. The effects of alloy composition and eutectic undercooling on eutectic morphology and eutectic nucleation mode were investigated. The simulated results were compared with those obtained experimentally.     

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).