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At least 19 records

Macrosegregation and nucleation in undercooled Pb-Sn alloys

A technique resulting in large undercoolings in bulk samples (23g) of lead-tin alloys was developed. Samples of Pb-12.5 wt percent Sn, Pb-61 wt percent Sn, and Pb-77 wt percent Sn were processed with undercoolings ranging from 4 to 34 K and with cooling rates varying between 0.04 and 4 K/sec. The nucleation behavior of the Pb-Sn system was found to be nonreciprocal. The solid Sn phase effectively nucleated the Pb phase of the eutectic; however, large undercoolings developed in Sn-rich eutectic liquid in the presence of the solid Pb phase. This phenomenon is believed to be mainly the result of differences in interfacial energies between solid Sn-eutectic liquid, and solid Pb-eutectic liquid rather than lattice misfit between Pb and Sn. Large amounts of segregation developed in the highly undercooled eutectic ingots. This macrosegregation was found to increase as undercooling increases. Macrosegregation in these undercooled eutectic alloys was found to be primarily due to a sink/float mechanism and the nucleation behavior of the alloy. Lead-rich dendrites are the primary phase in the undercooled eutectic system. These dendrites grow rapidly into the undercooled bath and soon break apart due to recalescence and Sn enrichment of the liquid. These fragmented Pb dendrites are then free to settle to the bottom portion of the ingot causing the macrosegregation observed in this study. A eutectic Pb-Sn alloy undercooled 20 K and cooled at 4 K/sec had a composition of about Pb-72 wt percent Sn at the top and 55 percent Sn at the bottom.

Degroh, Henry C., III↗

Macrosegregation and nucleation in undercooled Pb-Sn alloys

A novel technique resulting in large undercoolings in bulk samples (23 g) of lead-tin alloys was developed. Samples of Pb-12.5 wt percent Sn, Pb-61.9 wt.% Sn, and Pb-77 wt.% Sn were processed with undercoolings ranging from 4 to 34 K and with cooling rates varying between 0.04 and 4 K/s. The nucleation behavior of the Pb-Sn system was found to be nonreciprocal. The solid Sn phase effectively nucleated the Pb phase of the eutectic; however, large undercoolings developed in Sn-rich eutectic liquid in the presence of the solid Pb phase. This phenomenon is believed to be mainly the result of differences in interfacial energies between solid Sn-eutectic liquid, and solid Pb-eutectic liquid rather than lattice misfit between Pb and Sn. Large amounts of segregation developed in the highly undercooled eutectic ingots. This macrosegregation was found to increase as undercooling increases. Macrosegregation in these undercooled eutectic alloys was found to be primarily due to a sink/float mechanism and the nucleation behavior of the alloy. Lead-rich dendrites are the primary phase in the undercooled eutectic system. These dendrites grow rapidly into the undercooled bath and soon break apart due to recalescence and Sn enrichment of the liquid. These fragmented Pb dendrites are then free to settle to the bottom portion of the ingot causing the macrosegregation observed in this study. A eutectic Pb-Sn alloy undercooled 20 K and cooled at 4 K/s had a composition of about Pb-72 wt.% Sn at the top and 55% Sn at the bottom.

Degroh, Henry C., III↗

Undercooling and solidification behavior in the InSb-Sb system

Use of the droplet emulsion technique has been successful in studying the undercooling and crystallization behavior of Sb, InSb, and an InSb-Sb eutectic alloy. Both droplet size and imposed cooling rate were influential in controlling the extent of liquid undercooling. The droplet surface coating was of significant importance in determining the resultant solidification product structure through its effect on nucleation kinetics. The maximum undercooling for pure Sb was extended from 0.08 to 0.23 T sub m. While simple crushing techniques provided a dramatic increase in droplet undercooling over the bulk material, emulsification treatments both enhanced this undercooling and allowed successful formation of a metastable simple cubic Sb phase. This phase was stable to temperatures approaching the melting point. The simple cubic phase was detected in droplet samples processed using DTA, air and water quenching, and drop tube processing under a helium gas atmosphere. A deviation in the InSb parent ingot composition limited interpretation of the line compound results, however, emulsification techniques extended the undercooling of this material to 0.17 T sub L and provided a stable, protective surface coating for the droplets. Emulsification of the eutectic alloy was effective at producing various levels of undercooling from 0.1 to 0.2 T sub E. Microstructural examination revealed a normal-type eutectic structure in the undercooled droplets indicating that solidification occurred within the coupled zone and that this zone is somewhat symmetric about the eutectic composition.

Graves, J. A.↗

Macrosegregation in undercooled Pb-Sn eutectic alloys

A novel technique resulting in large undercoolings in bulk samples (23g) of lead-tin eutectic alloy is described. Samples of eutectic composition were processed with undercoolings ranging from 4 to 20 K and with cooling rates varying between 0.04 to 4 K/sec. The final macrostructure of undercooled samples depends on both the initial undercooling of the melt and the cooling rate. Gravity-driven segregation is found to increase with increasing undercooling. A eutectic Pb-Sn alloy undercooled at 20 K and cooled at 4 K/sec had a composition of about Pb-72 wt pct Sn at the top and 55 pct Sn at the bottom. Macrosegregation in these undercooled lead-tin eutectic alloys is shown to be primarily due to a sink/float mechanism caused by the difference in density of the solid and liquid phases and the undercooling and nucleation behavior of the alloy.

De Groh, H. C., III↗

Microstructures of undercooled germanium droplets

Undercoolings at crystal nucleation onset of liquid Ge droplets are measured and the microstructures of the droplets are examined. Undercooling values ranging from 150-415 + or 20 C were obtained. It is observed that for the samples undercooled less than 300 C prior to solidification the grain size was greater than 100 microns; for samples undercooled between 300-400 C the grain size was between 50-100 microns; and for samples undercooled greater than 400 C the grain size was 10-20 microns. Consideration is given to dendritic growth and interfacial undercooling. It is noted that there is a correlation between undercooling and as-crystallized grain structure.

Devaud, G.↗

Containerless processing of undercooled melts

Containerless drop tube processing allows for significant levels of liquid undercooling through control of parameters such as sample size, surface coating and cooling rate. A laboratory scale (3 m) drop tube has been developed which allows the undercooling and solidification behavior of powder samples to be evaluated under low gravity free-fall conditions. The level of undercooling obtained in an InSb-Sb eutectic alloy has been evaluated by comparing the eutectic spacing in drop tube samples with a spacing/undercooling relationship established using thermal analysis techniques. Undercoolings of 0.17 and 0.23 T(e) were produced by processing under vacuum and He gas conditions respectively. Alternatively, the formation of an amorphous phase in a Ni-Nb eutectic alloy indicates that undercooling levels of approximately 500 C were obtained by drop tube processing. The influence of droplet size and gas environment on undercooling behavior in the Ni-Nb eutectic was evaluated through their effect on the amorphous/crystalline phase ratio. To supplement the structural analysis, heat flow modeling has been developed to describe the undercooling history during drop tube processing, and the model has been tested experimentally.

Shong, D. S.↗

Dendritic growth and structure of undercooled nickel base alloys

The principal objectives of this overall investigation are to: study means for obtaining high undercooling in levitation melted droplets, and study structures produced upon the solidification of these undercooled specimens. Thermal measurements are made of the undercooling, and of the rapid recalescence, to develop an understanding of the solidification mechanism. Comparison of results is made with the modeling studies. Characterization and metallographic work is done to gain an understanding of the relationship between rapid solidification variables and the structures so produced. In ground based work to date, solidification of undercooled Ni-25 wt percent Sn alloy was observed by high-speed cinematography and the results compared with optical temperature measurements. Also in ground based work, 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. Measurements were carried out on samples at undercoolings up to 330 K. Microstructures of samples produced in ground based work were determined by optical metallography and by SEM, and microsegregation by electron microprobe measurements. A series of flight tests were planned to conduct experiments similar to the ground based experiments. The Space Shuttle Columbia carried an alloy undercooled experiment in the STS 61-C mission in January 1986. A sample of Ni-32.5 wt percent Sn eutectic was melted and solidified under microgravity conditions.

Flemings, M. C.↗

Droplet Growth in Undercooled Cu-Co Alloys

High undercooling usually leads to the refinement of microstructures, while an opposite tendency occurs in liquid immiscible alloys. In the Cu-Co system, there is a metastable liquid miscibility gap which may allow the study of droplet nucleation and growth by undercooling experiments. In the present work, two alloys of Cu50Co50 and Cu68Co32 (atomic) were undercooled using a melt fluxing technique in which the liquid separation temperature could be directly measured. It was observed that after separation the resultant melts were further undercooled by 315 K prior to solidification. The relationship between the largest droplet radius and undercooling was found to exhibit three regimes: a power law growth, linear growth, and saturation stage. In addition to dendrites and droplet-like morphology reported previously, an interconnected structure was formed for the Cu50Co50 alloy at intermediate undercooling. It played a crucial role in droplet coarsening at high undercooling.

Robinson, Michael B.↗

Containerless undercooling and solidification in drop tubes

A containerless low-gravity environment, produced within a 32 m drop tube apparatus, has been used to undercool and solidify metals, alloys or glasses by eliminating crucible induced nucleation processes. Niobium droplets with diameters in the range of 2 to 5 mm have been undercooled by 525 K which corresponds to the maximum undercooling reported by Turnbull and others on fine dispersions of low melting point metals. Solidification at large undercooling resulted in single crystalline spheres with the formation of interdendritic shrinkage channels on the sample surface rather than interior shrinkage cavities. The grain refinement as observed for Ni samples undercooled and solidified in fused silica crucibles does not occur in free-falling drops of Nb. A calculated solidification speed of undercooled Nb is compared to Ni. A solidification speed of 320 m/s is found for the Nb drops. This solidification speed is greater than or comparable to the solidification speeds calculated in splat cooled samples. Thus, a drop tube apparatus can be useful in the preparation and study of high temperature metastable compounds or alloys in bulk form.

Lacy, L. L.↗

Comparison of structures of gas atomized and of emulsified highly undercooled Ni-Sn alloy droplets

A comparison is made of microstructures of droplets of Ni-Sn alloys rapidly solidified by gas atomization and in a glass emulsifying medium. Cooling rate of the gas atomized particles ranged from 10 to the 3rd to 10 to the 6th K/s depending on droplet diameter (20-230 microns). In the hypoeutectic alloy studied, /Ni-(25 wt pct Sn)/, most particles showed a dendritic structure. These same particles, melted and resolidified in a glass medium using DTA (Differential Thermal Analysis), showed undercoolings up to 280 K: the structures were dendritic at low undercoolings and nondendritic at undercoolings above 220 K. It is concluded that the gas atomized particles exhibited little or no undercooling before nucleation; the solidification time of the undercooled emulsified droplets is substantially less than that of gas atomized droplets, and the undercooling required to achieve nondendritic structure depends on sample size.

Yamamoto, M.↗

Undercooling of acoustically levitated molten drops

It was observed that the acoustically levitated molten SCN (succinonitrile) drops can generally be undercooled to a degree where the impurities in the drop are responsible for the nucleation of the solid phase. However, it was also observed that ultrasound occasionally terminates undercooling of the levitated drops by initiating the nucleation of the solid at an undercooling level which is lower than that found for the nucleation catalyzed by the impurities in the drop. This premature nucleation can be explained by thermodynamic considerations which predict an increase in effective undercooling of the liquid upon the collapse of cavities. Pre-existing gas microbubbles which grow under the influence of ultrasound are suggested as the source of cavitation. The highly undercooled SCN drops can be utilized to measure the growth velocity of the solid in the deeply undercooled region including the hypercooled region.

Ohsaka, K.↗

A Method Based on Radiative Cooling for Detecting Structural Changes in Undercooled Metallic Liquids

We introduce a structure-sensitive parameter for undercooled melts which can be measured in containerless processing experiments. We have established that the ratio, R(T), of hemispherical total emissivity epsilon(sub T)(T) to constant-pressure specific heat c(sub p)(T) can serve as an indicator which is sensitive to any changes in short range atomic order in undercooled metallic melts. R(T) (triple bonds) epsilon(sub T)(T)/c(sub p)(T) values for nickel, zirconium, and silicon have been obtained using the high temperature electrostatic levitator while the levitated melts were undergoing purely radiative cooling into the deeply undercooled region. R(T) plots for undercooled liquid nickel and zirconium indicate no significant change in short-range structure from their melting temperatures to 15% undercooling. In contrast, liquid silicon shows marked short-range structural changes beginning above its melting temperature and extending throughout the undercooled region. The short-range structure of liquid silicon is related to the highly-directional covalent bonding which characterizes its solid form. The nickel and zirconium data show that epsilon(sub T) varies linearly with T, in support of metal emissivity theories.

Rulison, Aaron J.↗

Measurement of Interfacial Undercooling in a Dilute Pb-Sn Alloy Near the Regime of Morphological Instability

The solid/liquid (s/1) interfacial Seebeck technique was used to measure interfacial undercooling in a Pb-1 wt.% Sn alloy. For plane front solidification an undercooling in the range of 0.54-0.57C was recorded. However, for growth velocities between 6 to 15 micron/s the undercooling, increased with increase in velocity. 'Tbis is in contradiction to the theoretical predictions based on growth at the extremum condition. A modified analytical expression was developed based on the maro,,inal stability criterion to predict undercooling for growth velocities immediately over the limit of morphological stability. Between 6 to 15 microns/s the trend predicted by this modified expression is in qualitative agreement with the experimental results. This model is more consistent with the analysis of Venugopal and Kirkaldy which states that the extremum condition criterion is not applicable in the marginal stability regime. At higher growth velocities between 20 and 50 microns/s where stable cellular growth is expected the undercooling, decreased with increase in velocity. The predictions of Burden and Hunt based on extremum criterion agree reasonably well with the experimental results in this velocity range. Finally, the importance of non-equilibrium phase diagram parameters such as partition coefficient and liquidus slope were also evaluated using the experimental undercooling results obtained in this investigation.

Sen, S.↗

Studies of Nucleation and Growth, Specific Heat and Viscosity of Undercooled Melts of Quasicrystal and Polytetrahedral-Phase Forming Alloys

From extensive ground based work on the phase diagram and undercooling studies of Ti-Zr-Ni alloys, have clearly identified the composition of three different phases with progressively increasing polytetrahedral order such as, (Ti/Zr), the C14 Laves phase, and the i-phase, that nucleate directly from the undercooled liquid. The reduced undercooling decreases progressively with increasing polytetrahedral order in the solid, supporting Frank s hypothesis. A new facility for direct measurements of the structures and phase transitions in undercooled liquids (BESL) was developed and has provided direct proof of the primary nucleation of a metastable icosahedral phase in some Ti-Zr-Ni alloys. The first measurements of specific heat and viscosity in the undercooled liquid of this alloy system have been completed. Other than the importance of thermo-physical properties for modeling nucleation and growth processes in these materials, these studies have also revealed some interesting new results (such as a maximum of C(sup q, sub p) in the undercooled state). These ground-based results have clearly established the necessary background and the need for conducting benchmark nucleation experiments at the ISS on this alloy system.

Kelton, K. F.↗

Investigation of the Relationship between Undercooling and Solidification Velocity

This work was aimed at reconciling the differences between experimental measurements of the theoretical predictions of the solidification velocity as a function of undercooling. The theory proposed by Boettinger, Coriell and Trivedi (the BCT theory) has been one of the most widely used models for describing the nature of the solidification of undercooled metals and alloys. However, for undercoolings greater than about 5% of the absolute melting temperature, there is considerable discrepancy between theory and experiment. At these large undercoolings, experimental results exhibit a much lessened dependency of solidification velocity on undercooling than is predicted by theory. Furthermore, unpredicted plateaus in the solidification velocity as a function of undercooling are observed.

Bayuzick, Robert J.↗

Measurements of Dendritic Growth Velocities in Undercooled Melts of Pure Nickel Under Static Magnetic Fields

Dendritic growth velocities in undercooled melts of pure Ni have been intensively studied over the past fifty years. However, the literature data are at marked variance with the prediction of the widely accepted model for rapid dendritic growth both at small and at large undercoolings. In the present work, bulk melts of pure Ni samples of high purity were undercooled by glass fluxing treatment under a static magnetic field. The recalescence processes of the samples at different undercoolings were recorded using a high-speed camera, and were modeled using a software to determine the dendritic growth velocities. The present data confirmed the effect of melt flow on dendritic growth velocities at undercoolings below 100 K. A comparison of the present data with previous measurements on a lower purity material suggested an effect of impurities on dendritic growth velocities at undercoolings larger than 200 K as well.

Gao, Jianrong↗

(abstract) Determination of the Specific Heat and Total Hemispherical Total Emissivity of the Highly Undercooled Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) Alloy

High temperature high vacuum electrostatic levitation was combined with DSC experiments to determine the specific heat C(sub p) of the undercooled Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) liquid as a function of temperature. The containerless approach made it possible to undercool the melt to the glass transition temperature without inducing nucleation. Because the cooling process was purely radiative, noncontact temperature measurement techniques could be used to determine the specific heat to total hemispherical emissivity ratio, C(sub p)/epsilon(sub t), for the undercooled liquid region. Using C(sub p) values which were independently obtained by DSC, epsilon(sub t) could be determined. With knowledge of C(sub p) of the undercooled liquid it was possible to determine other thermodynamic properties such as Gibbs free energy and entropy as a function of undercooling.

levitation thermodynamic properties undercooled al↗

Undercooling measurement in a low-gravity containerless environment

A technique is described for measuring the amount of undercooling for samples processed in a low-gravity containerless environment. The time of undercooling is determined by measuring the time of cooling before nucleation and recalescence by two infrared detectors. Once the cooling curve for each drop is calculated, the amount of undercooling can then be found. The technique is demonstrated by measuring the amount of undercooling for drops of pure niobium and select compositions of the niobium-germanium alloy system while free falling in a 32 n evacuated drop tube. The total hemispherical emissivities and specific heats for these materials were measured using a high-temperature containerless calorimeter. An overview of the effect of undercooling on drops of niobium and niobium-germanium is given.

Robinson, M. B.↗