High-rate growth-mode transitions in Al-Si eutectics

Irregular eutectic growth in an aluminum-silicon alloy is investigated using directional solidification. The high-rate transition from flake to fiber morphology is characterized in term of the three dimensional microstructure. The transition is observed to occur over the velocity range from 100 to 1000 mm/s, and two regimes of behavior are observed using a characteristic length scale defined by the spatial variation in local volume fraction

Three-dimensional crystal-melt Wulff-shape and interfacial stiffness in the Al-Sn binary system

The quantitative determination of the three-dimensional Wulff shape for a metallic crystal-melt system is reported here. The anisotropy of crystal-melt interfacial free energy is experimentally measured for the Al–Sn binary system at temperatures of 300 and 500°C. Equilibrium shapes of liquid droplets entrained within the crystalline phase are measured experimentally on sequential two-dimensional sections, and the three-dimensional Wulff plot is reconstructed. For this system, it is found that a single-parameter description of anisotropy is not sufficient, and the anisotropy is reported using the leading terms of the relevant cubic harmonics. Accordingly, the anisotropy coefficients are determined to be ε1=(1.81±0.36)×10−2 and ε2=(−1.12±0.13)×10−2. In addition, the corresponding normal stiffness components as well as a generalized stiffness are quantified and compared with available predictions from atomistic simulations

The role of melt pool behavior in free-jet melt spinning

The influence of melt pool behavior on the competition between the nucleation of crystalline solidification products and glass formation is examined for an Fe-Si-B alloy. High-speed imaging of the melt pool, analysis of ribbon microstructure, and measurement of ribbon geometry and surface character all indicate upper and lower limits for melt spinning (MS) rates for which fully amorphous ribbons can be achieved. Comparison of the relevant time scales reveals that surface-controlled melt pool oscillation may be the dominant factor governing the onset of unsteady thermal conditions accompanied by varying amounts of crystalline nucleation observed near the lower limit. At high rates, the influence of these oscillations is minimal due to very short melt pool residence times. However, microstructural evidence suggests that the entrapment of gas pockets at the wheel-metal interface may play a critical role in establishing the upper rate limit. An observed transition in wheel-side surface character with an increasing MS rate supports this contention

Thermodynamic Treatment of Undercooled Cu-Mg Liquid and the Limits for Partitionless Crystallization

The thermodynamic properties of the binary Cu-Mg system are examined with a focus on equilibria involving the liquid phase, which is described with a four-species association model, incorporating a two-state treatment for the pure component liquids below their respective melting temperatures. The terminal and intermediate crystalline phases are described as substitutional solid solutions, employing two sublattices for the latter. Model parameters are fitted using available experimental data, and the resulting phase diagram is reported over the full range of compositions in the binary system. We also report the associated T 0 curves, indicating the limits of partitionless crystallization and compare these with reports of amorphous solid formation during rapid solidification processing

Energetics of nonequilibrium solidification in Al-Sm

Solution-based thermodynamic modeling, aided by first-principles calculations, is employed here to examine phase transformations in the Al-Sm binary system which may give rise to product phases that are metastable or have a composition that deviates substantially from equilibrium. In addition to describing the pure undercooled Al liquid with a two-state model that accounts for structural ordering, thermodynamic descriptions of the fcc phase, and intermediate compounds (Al4Sm-β, Al11Sm3-α, Al3Sm-δ, and Al2Sm-σ) are reanalyzed using special quasirandom structure and first-principles calculations. The possible phase compositions are presented over a range of temperatures using a “Baker-Cahn” analysis of the energetics of solidification and compared with reports of rapid solidification. The energetics associated with varying degrees of chemical partitioning are quantified and compared with experimental observations of the metastable Al11Sm3-α primary phase and reports of amorphous solids

In Situ Observation of Antisite Defect Formation during Crystal Growth

In situ x-ray diffraction (XRD) coupled with molecular dynamics (MD) simulations have been used to quantify antisite defect trapping during crystallization. Rietveld refinement of the XRD data revealed a marked lattice distortion which involves an a axis expansion and a c axis contraction of the stable C11b phase. The observed lattice response is proportional in magnitude to the growth rate, suggesting that the behavior is associated with the kinetic trapping of lattice defects. MD simulations demonstrate that this lattice response is due to incorporation of 1% to 2% antisite defects during growth

Enthalpy of Mixing in Al–Tb Liquid

The liquid-phase enthalpy of mixing for Al–Tb alloys is measured for 3, 5, 8, 10, and 20 at% Tb at selected temperatures in the range from 1364 to 1439 K. Methods include isothermal solution calorimetry and isoperibolic electromagnetic levitation drop calorimetry. Mixing enthalpy is determined relative to the unmixed pure (Al and Tb) components. The required formation enthalpy for the Al3Tb phase is computed from first-principles calculations. Based on our measurements, three different semi-empirical solution models are offered for the excess free energy of the liquid, including regular, subregular, and associate model formulations. These models are also compared with the Miedema model prediction of mixing enthalpy

Phase Stability for the Pd-Si System: First-Principles, Experiments, and Solution-Based Modeling

The relative stabilities of the compounds in the binary Pd-Si system were assessed using first-principles calculations and experimental methods. Calculations of lattice parameters and enthalpy of formation indicate that Pd5Si-μPd5Si-μ, Pd9Si2-αPd9Si2-α, Pd3Si-βPd3Si-β, Pd2Si-γPd2Si-γ, and PdSi-δPdSi-δ are the stable phases at 0 K (–273 °C). X-ray diffraction analyses (XRD) and electron probe microanalysis (EPMA) of the as-solidified and heat-treated samples support the computational findings, except that the PdSi-δPdSi-δ phase was not observed at low temperature. Considering both experimental data and first-principles results, the compounds Pd5Si-μPd5Si-μ, Pd9Si2-αPd9Si2-α, Pd3Si-βPd3Si-β, and Pd2Si-γPd2Si-γ are treated as stable phases down to 0 K (−273 °C), while the PdSi-δPdSi-δ is treated as being stable over a limited range, exhibiting a lower bound. Using these findings, a comprehensive solution-based thermodynamic model is formulated for the Pd-Si system, permitting phase diagram calculation. The liquid phase is described using a three-species association model and other phases are treated as solid solutions, where a random substitutional model is adopted for Pd-fcc and Si-dia, and a two-sublattice model is employed for Pd5Si-μPd5Si-μ, Pd9Si2-αPd9Si2-α, Pd3Si-βPd3Si-β, Pd2Si-γPd2Si-γ, and PdSi-δPdSi-δ. Model parameters are fitted using available experimental data and first-principles data, and the resulting phase diagram is reported over the full range of compositions

Thermodynamic limits of crystallization and the prediction of glass formation tendency

We have calculated the T0 curves for several Al-rare-earth binary alloys to assess the importance of the transport-based resistance to crystallization in the overall glass formation process and the general effectiveness of thermodynamic prediction of glass-forming ability. Our results show that the experimentally observed glass-forming compositions for Al-(Ce, Gd, Ho, Nd, Y, Dy) alloys strongly correlate with the composition range bounded by the T0curves associated with the relevant crystalline phases. This indicates that sluggish material transport, together with the tendency for clustering and other types of ordering at medium-range scale, is a key factor governing glass formation in these systems

Modeling of Thermodynamic Properties and Phase Equilibria for the Cu-Mg Binary System

The phase equilibria associated with the binary Cu-Mg system are analyzed by applying results from first-principles calculations to a general solution thermodynamics treatment. Differing from previously reported models, we employ a four-species association model for the liquid, while the terminal and intermediate solid phases are modeled as substitutional solutions with one or two sublattices, respectively. The zero-Kelvin enthalpies of formation for the intermediate compounds, Cu2Mg-C15 (cF24) and CuMg2-Cb (oF48) are computed using the Vienna Ab-initio Simulation Package (VASP). The Gibbs free energy functions for the individual phases are evaluated, and the resulting binary phase diagram is presented over the full composition range. While the phase diagram we propose exhibits only modest deviation from previously reported models of phase equilibria, our treatment provides better agreement with experimental reports of heat capacity and enthalpy of mixing, indicating a more self-consistent thermodynamic description of this binary system