High-Speed imaging and analysis of the solidification of undercooled nickel melts

Rapid solidification of undercooled pure nickel has been imaged at sufficiently high spatial resolution (64 ×X 64 pixels) and temporal resolution (40,500 frames/s) to observe interface shape and motion at solidification velocities exceeding 45 m/s. Imaging was of 8 g, quartz-enclosed melts at undercoolings of 70 to 300 K. Dendrite velocities within the melt were calculated from the surface velocities observed employing a simple geometric model of growth. Solidification was found to proceed invariably from a single nucleation point; growth velocity then followed an approximate power-law relationship with respect to undercooling up to some critical value ΔT*, where 150 K < ΔT* < 180 K. At higher undercoolings, velocity increased less rapidly than predicted by the power-law relationship and the interface morphology changed in appearance from angular to macroscopically smooth.     

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

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

Theoretical treatment of the solidification of undercooled Fe-Cr-Ni melts

The solidification behavior of undercooled Fe-Cr-Ni melts is analyzed with respect to the competitive formation of body-centered cubic (bcc) phase (ferrite) and face-centered cubic (fcc) phase (austenite). The activation energies of homogeneous nucleation and growth velocities for both phases as functions of undercooling of the melt are calculated on the basis of current theories of nucleation and dendrite growth using data of thermodynamic properties available in the literature. As model systems for numerical calculations, the alloys Fe-18.5Cr-11Ni forming primary ferrite and Fe-18.5Cr-12.5Ni forming primary austenite under near-equilibrium solid-ification conditions are considered. Nucleation of the bcc phase is always promoted in the under-cooled primary ferrite alloy, whereas the barrier for bcc nucleation falls below that for fcc nucleation for large undercooling in primary austenite alloys. With rising undercooling, tran-sitions of the fastest growth mode were found from bcc to fcc and subsequently from fcc to bcc for the primary ferrite forming alloy and from fcc to bcc for the primary austenite forming alloy. The results of the calculations provide a basis for understanding contradictory experi-mental findings reported in the literature concerning phase selection in rapidly solidified stainless steel melts for different process conditions. Formerly Visiting Scientist at the Institut fur Raumsimulation     

Solidification of highly undercooled Fe-P alloys

Rapid solidification behavior of highly undercooled iron-phosphorus alloys was investigated by using a high-speed optical temperature measurement system. The experimental results on solidification rate as a function of bulk undercooling agree well with a model which includes a treatment of nonequilibrium effects during the solidification process. The model is based on an earlier analysis by Boettinger, Coriell, and Trivedi_[81] (BCT) and employs temperature-dependent values of equilibrium liquidus slope, equilibrium solute distribution coefficient, and solute interdiffusion coefficient. Values of the kinetic parameters,a ₀ andV ₀ , in the analysis which best fit the experimental results are 5 x 10_-10 m and 600 m/s, respectively. Comparison of experimental results and theory suggests that a transition from local equilibrium to nonequilibrium solidification takes place with increasing undercooling and that interface kinetic effects become predominant at higher undercooling (or growth velocity).     

Fragmentation of faceted dendrite in solidification of undercooled B-doped Si melts

The fragmentation of the faceted dendrite of B-doped Si solidified from the undercooled melt was investigated using an electromagnetic levitator. The 〈110〉 dendrites, which grew at ΔT <∼100 K, never fragmented because they were composed of {111} planes with the lowest interface energy. On the other hand, the 〈100〉 dendrites, which grew at ΔT>∼100 K, showing fourfold axial symmetry, broke up into small pieces at undercoolings of more than 200 K. It was suggested that the capillary force acts on the interface with a relatively high energy to break up the dendrite into small pieces, since the 〈100〉 dendrites are composed of {110} and {100} planes with interface energies larger than that of the {111} plane. Moreover, striations of concentric circles formed by the segregation of B revealed that the remaining melt solidifies from the surface toward the center to engulf the fragmented dendrites. This solidification process seems different from those of typical metallic materials, in which the fragmented dendrites are randomly distributed throughout the sample and the remaining liquid solidifies from the fragmented dendrites. This solidification characteristic was discussed in relation to the influence of electromagnetic force on the microstructure of Si.     

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.     

Nonequilibrium solidification of undercooled melt of Ag-Cu alloy entrained in the primary phase

The solidification structure of undercooled melt of Ag-Cu alloy, entrained in its primary Cu-rich phase, has been investigated. The undercooling procedure consisted of equilibration of a Cu-13 pct Ag alloy in the two-phase liquid-solid region, followed by repeated thermal cycling of the liquid. Slow cooling of the sample in the present work established the ability to undercool the melt up to 70 K below the eutectic temperature of this alloy. The microstructure of the undercooled alloy indicated a complete absence of eutectic reaction on subsequent quenching of the melt directly from the equilibration temperature. The compositional analysis of the constituent phases by electron probe microanalysis (EPMA) technique provided evidence for the massive diffusionless solidification of the undercooled liquid. The X-ray diffraction study and electron microscopic examination indicated evidence for the spinodal transformation of the metastable solid solution phase. The composition of the phases formed on decomposition matched well with the calculated coherent spinodal boundaries in this system. The evolution of the metastable microstructure in the mushy-state quenching process of this alloy is discussed.     

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.     

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.     

Measurements of the bulk velocity during solidification of metallic alloys

The ultrasound Doppler velocimetry (UDV) was applied to measure the bulk flow in a Sn-15 wt pct Pb alloy solidified directionally from a water-cooled copper chill. The flow is driven by a rotating magnetic field (RMF). Our results show that the velocity profiles undergo distinct modifications during solidification indicating the occurrence of more sophisticated flow patterns as known from the isothermal case. Furthermore, the UDV data allow an assessment of the current position of the dendritic solidification front. This research is supported by the Deutsche Forschungsgemeinschaft (DFG) in the form of the SFB 609 “Electromagnetic Flow Control in Metallurgy, Crystal Growth and Electrochemistry.” This support is gratefully acknowledged by the authors.     

The solidification of undercooled melts <Emphasis Type="Italic">via</Emphasis> twinned dendritic growth

The solidification of undercooled Cu-x wt pct Sn (x=1, 2, 3, or 4) alloys has been studied by a melt-encasement (fluxing) technique. It was found that below undercoolings of ΔT≈90 K, the preferred dendrite growth orientation in each of these alloys was along the 〈111〉 direction: moreover, the 2 and 3 wt pct Sn alloys also displayed evidence of twinned growth. Above ΔT≈90 K, the preferred growth direction returned to the more usual 〈100〉 orientation.     

The use of new PHACOMP in understanding the solidification microstructure of nickel base alloy weld metal

The weld metal microstructures of five commercial nickel base alloys (HASTELLOYS* C-4, C-22, and C-276, and INCONELS* 625 and 718) have been examined by electron probe microanalysis and analytical electron microscopy. It has been found that solidification terminates in many of these alloys with the formation of a constituent containing a topologically-close-packed (TCP) intermetallic phase(i.e., σ, P, Laves). Electron microprobe examination of gas-tungsten-arc welds revealed a solidification segregation pattern of Ni depletion and solute enrichment in interdendritic volumes. New PHACOMP calculations performed on these segregation profiles revealed a pattern of increasingM _d (metal-d levels) in traversing from a dendrite core to an adjacent interdendritic volume. In alloys forming a terminal solidification TCP constituent, the calculatedM _d values in interdendritic regions were greater than the criticalM _d values for formation ofσ as stated by Morinagaet al. Implications of the correlation between TCP phase formation andM _d in the prediction of weld metal solidification microstructure, prediction of potential hot-cracking behavior, and applications in future alloy design endeavors are discussed.     

The growth rate of dendrites in undercooled tin

The dendrite growth velocity has been determined for tin in melts undercooled as much as 40°C (approximately twice the maximum undercooling reported previously). The results can be represented approximately asV = 0.8 (ΔT) ² WhereV is the growth velocity in mm s⁻¹ and ΔT is the undercooling in degrees centrigrade.     

Constant-pressure specific heat to hemispherical total emissivity ratio for undercooled liquid nickel,Zirconium, and Silicon

Radiative cooling curves of nickel, zirconium, and silicon melts that were obtained using the high-temperature, high-vacuum electrostatic levitator (HTHVESL) have been analyzed to determine the ratio between the constant-pressure specific heat and the hemispherical total emissivity,c _p(T)/∈_T(T).This ratio determined over a wide liquid temperature range for each material allows us to determinec _p(T) if ∈_T (T) is known orvice versa.Following the recipe, the hemispherical total emissivities for each sample at its melting temperature, ∈_T (T) _m, have been determined usingc _p(T_m) values available in the literature. They are 0.15, 0.29, and 0.17, for Ni, Zr, and Si, respectively. AARON J. RULISON formerly with JPL, Pasadena, CA.