The surface tension and specific heat of stable and metastable liquid Ni70.2Si29.8 eutectic alloy were measured by electromagnetic levitation oscillating drop method and drop calorimetry. The surface tension depends on tempera- ture linearly within the experimental undercooling regime of 0―182 K (0.12 TE). Its value is 1.693 N·m?1 at the eutectic temperature of 1488 K, and the temperature coefficient is ?4.23×10?4 N·m?1·K?1. For the specific heat measurement, the maximum undercooling is up to 253 K (0.17 TE). The specific heat is determined as a polynomial function of tem- perature in the experimental temperature regime. On the basis of the measured data of surface tension and specific heat, the temperature-dependent density, excess volume and sound speed of liquid Ni70.2Si29.8 alloy are predicted theoreti- cally.
Bulk samples and small droplets of liquid Fe-10%Sb alloys are undercooled up to 429 K (0.24TL) and 568 K (0.32TL), respectively, with glass fluxing and free fall techniques. The high undercooling does not change the phase constitution, and only the αFe solid solution is found in the rapidly solidified alloy. The experimental results show that when the undercooling is below 296 K, the growth velocity of αFe dendrite rises exponentially with the increase of undercooling and reaches a maximum value 1.38 m/s. Subsequently, the growth velocity begins to decrease if undercooling further increases. The αFe phase grows into coarse dendrites under small undercooling conditions, whereas it becomes vermicular dendrites in highly undercooled melts. The solute trapping is closely related to the dendrite growth velocity and cooling rate rather than undercooling. Although the solute trapping can be remarkably suppressed by the rapid dendrite growth, the segregationless solidification is not observed in the present experiments due to the large solidification temperature range.
The metastable liquid phase separation occurs in the ternary Cu50Fe37.5Co12.5 peritectic alloy droplets during free fall. The separated alloy melt rapidly solidifies and evolves core-shell microstructure composed of L1(Cu) and L2(Fe,Co) phases. Based on the determination of the phase transition temperature, the core-shell microstructure evolution, the interfacial energy, the temperature gradient and the Marangoni migration are analyzed. The interfacial energy of the separated liquid phase increases with the decrease of the temperature. The temperature gradient changes from large to small along the radius direction from inside to outside in the alloy droplet. The Marangoni force (FM) acting on the micro-droplet of L2(Fe,Co) phase increases with the increase of the size of the L2(Fe,Co) phase, and decreases with the increase of undercooling. Driven by FM, the micro-droplet of L2(Fe,Co) phase migrates from outside to inside in the alloy droplet, collides and coagulates each other during migration, and then forms different types of core-shell microstructures.
The solidification characteristics of three types of Pb-Sb-Sn ternary alloys with different primary phases were studied under substantial undercooling conditions. The experimental results show that primary (Pb) and SbSn phases grow in the dendritic mode, whereas primary (Sb) phase exhibits faceted growth in the form of polygonal blocks and long strips. (Pb) solid solution phase displays strong affinity with SbSn intermetallic compound so that they produce various morphologies of pseudobinary eutectics, but it can only grow in the divorced eutectic mode together with (Sb) phase. Although (Sb) solid solution phase and SbSn intermetallic com- pound may grow cooperatively within ternary eutectic microstructures, they sel- dom form pseudobinary eutectics independently. The (Pb)+(Sb)+SbSn ternary eutectic structure usually shows lamellar morphology, but appears as anomalous eutectic when its volume fraction becomes small. EDS analyses reveal that all of the three primary (Pb), (Sb) and SbSn phases exhibit conspicuous solute trapping effect during rapid solidification, which results in the remarkable extension of sol- ute solubility.
The phase separation and dendrite growth characteristics of ternary Fe-43.9%Sn- 10%Ge and Cu-35.5%Pb-5%Ge monotectic alloys were studied systematically by the glass fluxing method under substantial undercooling conditions. The maximum undercoolings obtained in this work are 245 and 257 K, respectively, for these two alloys. All of the solidified samples exhibit serious macrosegregation, indicating that the homogenous alloy melt is separated into two liquid phases prior to rapid solidification. The solidification structures consist of four phases including α-Fe, (Sn), FeSn and FeSn2 in Fe-43.9%Sn-10%Ge ternary alloy, whereas only (Cu) and (Pb) solid solution phases in Cu-35.5%Pb-5%Ge alloy under different undercool- ings. In the process of rapid monotectic solidification, α-Fe and (Cu) phases grow in a dendritic mode, and the transition "dendrite→monotectic cell" happens when alloy undercoolings become sufficiently large. The dendrite growth velocities of α-Fe and (Cu) phases are found to increase with undercooling according to an exponential relation.
The liquid to solid transformation of ternary Ag42.4Cu21.6Sb36 eutectic alloy was ac- complished in an ultrasonic field with a frequency of 35 kHz, and the growth mechanism of this ternary eutectic was examined. Theoretical calculations predict that the sound intensity in the liquid phase at the solidification interface increases gradually as the interface moves up from the sample bottom to its top. The growth mode of (ε + θ + Sb) ternary eutectic exhibits a transition of "divorced eutectic— mixture of anomalous and regular structures—regular eutectic" along the sample axis due to the inhomogeneity of sound field distribution. In the top zone with the highest sound intensity, the cavitation effect promotes the three eutectic phases to nucleate independently, while the acoustic streaming efficiently suppresses the coupled growth of eutectic phases. In the meantime, the ultrasonic field accelerates the solute transportation at the solid-liquid interface, which reduces the solute solubility of eutectic phases.
The metastable liquid phase separation and rapid solidification of Cu60Fe30Co10 ternary peritectic alloy were investigated by using the drop tube technique and the differential scanning calorimetry method. It was found that the critical temperature of metastable liquid phase separation in this alloy is 1623.5 K, and the two sepa- rated liquid phases solidify as Cu(Fe,Co) and Fe(Cu,Co) solid solutions, respec- tively. The undercooling and cooling rate of droplets processed in the drop tube increase with the decrease of their diameters. During the drop tube processing, the structural morphologies of undercooled droplets are strongly dependent on the cooling rate. With the increase of the cooling rate, Fe(Cu,Co) spheres are refined greatly and become uniformly dispersed in the Cu-rich matrix. The calculations of Marangoni migration velocity (VM) and Stokes motion velocity (VS) of Fe(Cu,Co) droplets indicated that Marangoni migration contributes more to the coarsening and congregation of the minor phase during free fall. At the same undercooling, the VM/VS ratio increases drastically as Fe(Cu,Co) droplet size decreases. On the other hand, a larger undercooling tends to increase the VM/VS value for Fe(Cu,Co) drop- lets with the same size.
DAI FuPing, CAO ChongDe & WEI BingBo Department of Applied Physics, Northwestern Polytechnical University, Xi’an 710072, China
The evolution process of core-shell microstructures formed in monotectic alloys under the space environment condition was investigated by the numerical simula- tion method. In order to account for the effect of surface segregation on phase separation, Model H was modified by introducing a surface free energy term into the total free energy of alloy droplet. Three Fe-Cu alloys were taken as simulated examples, which usually exhibit metastable phase separation in undercooled and microgravity states. It was revealed by the dynamic simulation process that the formation of core-shell microstructures depends mainly on surface segregation and Marangoni convection. The phase separation of Fe65Cu35 alloy starts from a dispersed structure and gradually evolves into a triple-layer core-shell micro- structure. Similarly, Fe50Cu50 alloy experiences a structural evolution process of "bicontinuous phase → quadruple-layer core-shell → triple-layer core-shell", while the microstructures of Fe35Cu65 alloy transfer from the dispersed structure into the final double-layer core-shell morphology. The Cu-rich phase always forms the outer layer because of surface segregation, whereas the internal microstructural evolu- tion is controlled mainly by the Marangoni convection resulting from the tempera- ture gradient.
The high undercooling and rapid solidification of Ni-10%Cu-10%Fe-10%Co quaternary alloy were achieved by electromagnetic levitation and glass fluxing techniques. The maximum undercooling of 276 K (0.16TL) was obtained in the experiments. All the solidified samples are determined to be α-Ni single-phase solid solutions by DSC thermal analysis and X-ray diffraction analysis. The microstructure of the α-Ni solid solution phase transfers from dendrite to equiaxed grain with an increase in undercooling, accompanied by the grain refinement effect. When the undercooling is very large, the solute trapping effect becomes quite significant and the microseg-regation is suppressed. The experimental measure-ment of α-Ni dendrite growth velocity indicates that it increases with undercooling according to the relation, V=8×10?2×?T1.2.
The rapid solidification of Sb60Ag20Cu20 ternary alloy was realized by high under- cooling method, and the maximum undercooling is up to 142 K (0.18TL). Within the wide undercooling range of 40-142 K, the solidified microstructures are composed of (Sb), θ and ε phases. High undercooling enlarges the solute solubility of (Sb) phase, which causes its crystal lattice to expand and its crystal lattice constants to increase. Primary (Sb) phase grows in two modes: at small undercoolings non-faceted dendrite growth is the main growth form; whereas at large undercool- ings faceted dendrite growth takes the dominant place. The remarkable difference of crystal structures between (Sb) and θ phases leads to (θ + Sb) pseudobinary eutectic hard to form, whereas strips of θ form when the alloy melt reaches the (θ + Sb) pseudobinary eutectic line. The cooperative growth of θ and ε phases contrib- utes to the formation of (ε + θ ) pseudobinary eutectic easily. In addition, the crys- tallization route has been determined via microstructural characteristic analysis and DSC experiment.
