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.     

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.     

Solidification of undercooled Fe-Cr-Ni alloys: Part I. Thermal behavior

Solidification of undercooled Fe-Cr-Ni alloys was studied by high-speed pyrometry during and after recalescence of levitated, gas-cooled droplets. Alloys were of 70 wt pct Fe, with Cr varying from 15 to 19.7 wt pct, balance was Ni. Undercoolings were up to about 300 K. Alloys of Cr content less than that of the eutectic (18.1 wt pct) have face-centered cubic (fee) (austenite) as their equilibrium primary phase, and alloys of higher Cr content have body-centered cubic (bcc) (ferrite) as their equilibrium primary phase. However, except at low undercoolings in the hypoeutectic alloys, all samples solidified with bcc as the primary phase; the bcc then transformed to fcc during initial recalescence for the lower Cr contents or during subsequent cooling for the higher Cr contents. The bcc-to-fcc transformation, whether in the semisolid or solid state, was detected by a second recalescence. In the hypoeutectic alloys, the growth of primary metastable bcc apparently results from preferred nucleation of bcc. The subsequent nucleation of fcc may occur at bcc/bcc grain boundaries. Formerly Graduate Student, Department of Materials Science and Engineering, Massachusetts Institute of Technology     

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.     

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.     

Heterogeneous nucleation of solidification of Si by solid AI in hypoeutectic Al-Si alloy

Melt-spun Al-3 wt pct Si with and without ternary additions of Na and Sr has been heat-treated above the Al-Si eutectic temperature in a differential scanning calorimeter to form a microstructure of Al-Si eutectic liquid droplets embedded in the α-Al matrix. During subsequent cooling in the calorimeter, the heterogeneous nucleation temperature for solidification of Si in contact with the surrounding Al matrix depends sensitively on the alloy purity, with a nucleation undercooling which increases with increasing alloy purity from 9 to 63 K below the Al-Si eutectic temperature. These results are consistent with Southin’s hypothesis that low levels of trace P impurities are effective in catalyzing Si nucleation in contact with the surrounding Al matrix. With a low Al purity alloy, 0.1 wt pct Na addition increases the Si nucleation undercooling from 9 to 50 K, 0.15 wt pct Sr addition does not affect the Si nucleation temperature, and 0.3 wt pct Sr addition decreases the Si nucleation undercooling from 9 to 3 to 4 K. The solidified microstructure of the liquid Al-Si eutectic droplets embedded in the Al matrix depends on the Si nucleation undercooling. With low Si nucleation undercooling, each Al-Si eutectic liquid droplet solidifies to form one faceted Si particle; however, with high Si nucleation undercooling, each Al-Si eutectic droplet solidifies to form a large number of nonfaceted Si particles embedded in Al. Formerly with the Oxford Centre for Advanced Materials and Composites, Department of Materials, Oxford University     

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.     

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.     

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.     

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.     

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).     

Solidification of undercooled Sn-Sb peritectic alloys: Part I. Microstructural evolution

The droplet emulsion technique, which involves dispersal of a bulk liquid alloy into a collection of fine droplets (5 to 30μm), was applied to Sn-Sb alloys to yield high levels of controlled undercooling. The maximum undercooling levels achieved varied from 179 °C for pure Sn to 113 °C for a Sn-16 at. pct Sb alloy. Analysis of hypoperitectic alloy samples (alloys with an Sb content less than that of the liquid at the peritectic temperature) indicates that solute trapping occurs during solidification at the levels of undercooling and cooling rate investigated, yielding nearly homogeneousβ-tin solid solutions with compositions approaching those of the bulk alloys. With increasing undercooling and/or cooling rate, hyperperitectic alloys exhibit a transition from a highly segregated structure consisting of faceted primary intermetallic phase and cellularβ to a structure consisting primarily of a supersaturated tin-rich solid solution. Lattice constant measurements confirm that virtually complete supersaturation ofβ-tin was achieved in emulsion samples cooled at 200 °C s^s−1 for compositions up to approximately 20 at. pct Sb. The development and characteristics of subsequent solid-state precipitation were used to guide the interpretation of the often complex solidification reaction sequences in the hyperperitectic alloys. The formation of supersaturatedβ-tin solid solutions in the undercooled samples is related to the appropriate metastable phase equilibria and the development of solute trapping. Formerly Graduate Student, Department of Materials Science and Engineering, University of Wisconsin-Madison     

Microstructural development in undercooled lead- tin eutectic alloys

A model was developed to predict micro structural development in lead—61.9 wt pct Sn (eutectic) alloys which were undercooled 5 to 25 K below their equilibrium freezing temperature prior to being preferentially nucleated. While the initial solidification velocity rapidly increases with increasing undercooling, the model predicts it to quickly decrease, prior to 10 pct solid formation, after which growth continues near the equilibrium temperature. Experimentally, and in accordance with the prediction, the eutectic emanated from the nucleation site with an initially fine spacing that increased with distance. However, in contrast to the model, the eutectic grew outward in a spokelike manner with each arm surrounded by a globular structure, this being attributed to the difficulty of lateral nucleation. Microstructural uniformity was further compromised by equiaxed eutectic grains which grew ahead of the advancing interface in the now only slightly undercooled liquid. Consequently, while containerless techniques may ensure sample purity and permit processing of high-temperature materials, development of a continuously fine and uniformly aligned microstructure cannot be assumed. This article is based on a presentation made in the symposium entitled “Microgravity Solidification, Theory and Experimental Results” as a part of the 1993 TMS Fall meeting, October 17-21, 1993, Pittsburgh, PA, under the auspices of the TMS Solidification Committee.     

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.     

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.     

Effect of growth conditions on the structure of directionally solidified γlγ’δ eutectic

γ/γ/’-δ eutectic alloy containing 21.5 wt pct Nb, 2.5 wt pct Al, balance Ni was directionally solidified under a thermal gradient (G) of 500 K/cm and different schedules of growth rate (R). Under steady state growth rate conditions, the critical (G/R) for plane front solidification is 25 K h/cm². At progressively lower (G/R) the structure becomes richer in γ-phase,i.e. hypoeutectic. Sudden increase in growth speed causes the structure to change from lamellar to cellular and gradual increase in growth speed results in interlamellar spacings that are larger than the extremum values. Sudden decrease in growth speed causes little disturbance in the structure but causes the eutectic grain size to increase.     

Dendrite characteristics in directionally solidified Pb-8 Pct Au and Pb-3 Pct Pd alloys

Pb-8 pct Au and Pb-3 pct Pd alloy specimens partially directionally solidified and then quenched have been examined in order to characterize their dendritic microstructural details and solute composition profiles. Dendrite tip radii have been measured by a controlled sectioning technique. Dendrite tip radius, solute content of quenched liquid at the dendrite tip, solute profile within the interdendritic region and ahead of the dendrite tip, cell length, and the primary arm spacing values obtained experimentally have been compared with the theoretical predictions. Two groups of models, one based on the minimum undercooled dendrite tip criterion and the other based on the marginal stability at the dendrite tip, have been examined. The Burden and Hunt model, based on the “minimum undercooling” approach, does not predict the observed behavior. However, a modification of the Burden and Hunt's model recently proposed by Laxmanan shows a good fit to the experimentally observed parameters. The models based on the marginal stability approach also predict most of the observed behavior well. It is concluded that quantitative comparison of the primary arm spacing measurements can not form the basis of distinguishing among the various dendrite growth models in a positive temperature gradient. There is a critical need to carry out carefully controlled directional solidification experiments in a well characterized metallic alloy system to help distinguish between the minium dendrite tip undercooling and the marginal stability approaches. New experiments based on simultaneous measurements of (a) dendrite tip radius, (b) dendrite tip temperature, and (c) the solute profile ahead of the dendrite tip—all in a convection free atmosphere—are required.     

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.     

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.