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.     

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.     

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.     

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     

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.     

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.     

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.     

Influence of Phosphorus on the Nucleation of Eutectic Silicon in Al-Si Alloys

The role of phosphorus (P) in the heterogeneous nucleation of eutectic silicon (Si) and the evolution of eutectic grains in hypoeutectic aluminum-silicon alloys were investigated. Systematic additions of P in the range of 0.5 to 20 ppm to Al-7 wt pct Si alloys of different purities have shown that the morphology of the eutectic Si changes from a fine plate- to a coarse flake-like structure. The growth of eutectic grains was investigated by interrupting the eutectic reaction by quenching experiments. Moreover, the macroscopic growth mode of the eutectic grains was characterized by electron backscatter diffraction. An increase in P concentration from 2 to 3 ppm resulted in a transition of the macroscopic growth mode of the Al-Si eutectic in high purity alloys from growth with a planar front with a strong dependence of the thermal gradient, to nucleation in the vicinity of the primary Al dendrites and subsequent growth of distinct eutectic grains. It is suggested that AlP particles are the key impurities acting as potential nucleation sites for eutectic Si. This is further substantiated as with increasing P concentration nucleation and growth of the Al-Si occurred at higher temperatures close the equilibrium Al-Si eutectic solidification temperature at 850 K (577 °C). In addition, the recalescence undercooling ΔT _R,eu was reduced from 4.5 K (0.5 ppm P) to 1.5 K (20 ppm P) in high purity alloys. This was accompanied by a drastic increase of the nucleation rate of the eutectic grains.     

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     

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     

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).     

Solidification behavior,microstructure and silicon twinning of Al-10Si alloys with ytterbium addition

The solidification behavior, micro structure and silicon twinning of Al-10 Si alloys with Yb addition were investigated by thermal analysis, optical microscopy, X-ray diffraction. scanning electron microscopy, and transmission electron microscopy. The results indicate that the nucleation temperature, minimum temperature, and growth temperature of Al-lOSi alloys decrease with increasing Yb content. The cooling curves of the Yb-modified alloys exhibit marked recalescence. The recalescence of the modified alloy peaks at 2.3 ℃ when the Yb content is 0.7 wt%. The 3 D morphologies of eutectic Si in Yb-modified alloys change from a coarse plate-like structure to a honeycomb structure with many fine fibrous structures.The Al-Si-Yb intermetallic compound is observed in the 1.0 wt% Yb-modified alloy. Meanwhile, XRD analysis and TEM results indicate that the average twin spacing in the Yb-modified alloys is 18-46.2 nm.The average twin spacing of eutectic Si decreases with increasing Yb content. When the Yb content in the modified alloy is increased to 0.7 wt%, the average twin spacing value of eutectic Si reaches to 18 nm,which promotes the formation of twins and refinement of eutectic Si.     

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.     

Experimental and Numerical Modeling of Segregation in Metallic Alloys

Electromagnetic levitation (EML) has been used as an experimental technique for investigating the effect of the nucleation and cooling rate on segregation and structure formation in metallic alloys. The technique has been applied to aluminum-copper alloys. For all samples, the primary phase nucleation has been triggered by the contact of the levitated droplet with an alumina plate at a given undercooling. Based on the recorded temperature curves, the heat extraction rate and the nucleation undercooling for the primary dendritic and the secondary eutectic structures have been determined. Metallurgical characterizations have consisted of composition measurements using a scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometry and the analysis of SEM images. The distribution maps drawn for the composition, the volume fraction of the eutectic structure, and the dendrite arm spacing (DAS) reveal strong correlations. Analysis of the measurements with the help of a cellular-automaton (CA)–finite-element (FE) model is also proposed. The model involves a new coupling scheme between the CA and FE methods and a segregation model accounting for diffusion in the solid and liquid phases. Extensive validation of the model has been carried out on a typical equiaxed grain configuration, i.e., considering the free growth of a mushy zone in an undercooled melt. It demonstrates its capability of dealing with mass exchange inside and outside the envelope of a growing primary dendritic structure. The model has been applied to predict the temperature curve, the segregation, and the eutectic volume fraction obtained upon single-grain nucleation and growth from the south pole of a spherical domain with and without triggering of the nucleation of the primary solid phase, thus simulating the solidification of a levitated droplet. Predictions permit a direct interpretation of the measurements.     

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

     

Solidification of undercooled Sn-Sb peritectic alloys: Part II. Heterogeneous nucleation

The undercooling behavior of fine droplet samples of Sn-rich, Sn-Sb alloys was investigated using differential thermal analysis (DTA). Undercooling levels measured during cooling from the liquid state follow the trend of the intermetallic phase liquidus, suggesting that solidification of all droplet samples (even those which solidify to yield a supersaturatedβ-tin product) was probably initiated with formation of primary intermetallic phase. Heterogeneous nucleation thermal cycling treatments were then used to measure the relative catalytic potency of primary intermetallic phases in this system for nucleation ofβ-tin during cooling. Crystallization reactions below the equilibrium peritectic temperature of 250 °C, at 187 °C and 230 °C, have been interpreted as corresponding to nucleation ofβ on Sn₃Sb₂ and SnSb substrates, respectively. The behavior observed in the Sn-Sb system can be generalized to guide the interpretation of heterogeneous catalysis and the analysis of solidification pathways in other peritectic alloy systems. Formerly Graduate Student, Department of Materials Science and Engineering, University of Wisconsin-Madison     

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.