Rapid solidification of bulk Ag42.4Cu21.6Sb36 ternary eutectic alloy is accomplished by glass fluxing method,during which the maximum undercooling attains 114 K (0.16 TE). Under high undercooling conditions,the ternary eutectic consists ofε (Ag3Sb),(Sb)and θ(Cu2Sb)phases,instead of (Ag),(Sb)and θphases as predicted by the phase diagram.In the sample of small undercooling,the alloy microstructure is characterized by the mixture of primary θ(Cu2Sb),(ε+θ) and (ε+Sb) pseudobinary eutectics,and regular (ε+θ+Sb) ternary eutectic.With the increase of undercooling, θ (Cu2Sb) primary phase and pseudobinary eutectics disappear gradually,and ternary eutectic transfers from regular to anomalous structure.When undercooling exceeds 102 K,anomalous (ε+θ+Sb) ternary eutectic is the unique microstructure.Competitive nucleation and growth of these three eutectic phases is the main cause for the formation of complex growth morphologies.Based on the current experiments and theoretical calculations,it can be concluded that the intermetallic compound phaseθ(Cu2Sb) is the leading nucleating phase.
Rapid growth behavior of ■ phase has been investigated in the undercooling experiments of Cu-14%Ge, Cu-15%Ge, Cu-18.5%Ge and Cu-22%Ge alloys. Alloys of the four compositions obtain the maximum undercoolings of 202 K(0.17TL), 245 K(0.20TL), 223 K(0.20TL) and 176 K(0.17TL), respectively. As the content of Ge increases, the microstructural transition of "α (Cu) dendrite + ■ peritectic phase →■ peritectic phase →■ dendrite + (ε +■ ) eutectic" takes place in the alloy at small undercooling, while the microstructural transition of "fragmented α (Cu) dendrite + ■ peritectic phase →■peritectic phase →■ dendrite + ε phase" happens in the alloy at large undercooling. EDS analysis of the Ge content in ■ peritectic phase indicates that undercooling enlarges the solid solubility of α dendrite, which leads to a decrease in the Ge content in ■ phase as undercooling increases. In the Cu-18.5%Ge alloy composed of ■ peritectic phase, the Ge content in ■ phase increases when undercooling increases, which is due to the restraint of the Ge enrichment on the grain boundaries by high undercooling effect.
The specific heat and related thermophysical properties of liquid Fe77.5Cu13Mo9.5 monotectic alloy were investigated by an electromagnetic levitation drop calo-rimeter over a wide temperature range from 1482 to 1818 K.A maximum under-cooling of 221 K(0.13 Tm)was achieved and the specific heat was determined as 44.71 J·mol1·K1.The excess specific heat,enthalpy change,entropy change and Gibbs free energy difference of this alloy were calculated on the basis of experimental results.It was found that the calculated results by traditional esti-mating methods can only describe the solidification process under low under-cooling conditions.Only the experimental results can reflect the reality under high undercooling conditions.Meanwhile,the thermal diffusivity,thermal conductivity,and sound speed were derived from the present experimental results.Furthermore,the solidified microstructural morphology was examined,which consists of(Fe)and(Cu)phases.The calculated interface energy was applied to exploring the correlation between competitive nucleation and solidification microstructure within monotectic alloy.
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.
