Solidification of Highly Undercooled Hypereutectic Ni-Ni3B Alloy Melt

The solidification of undercooled Ni-4.5 wt pct B alloy melt was investigated by using the glass fluxing technique. The alloy melt was undercooled up to ΔT _p ~ 245 K (245 °C), where a mixture of α-Ni dendrite, Ni₃B dendrite, rod eutectic, and precipitates was obtained. If ΔT _p < 175 K ± 10 K (175 °C ± 10 °C), the solidification pathway was found as primary transformation and eutectic transformation (L → Ni₃B and L → Ni/Ni₃B); if ΔT _p ≥ 175 K ± 10 K (175 °C ± 10 °C), the pathway was found as metastable eutectic transformation, metastable phase decomposition, and residual liquid solidification (L → Ni/Ni₂₃B₆, Ni₂₃B₆ → Ni/Ni₃B, and L_r → Ni/Ni₃B). A high-speed video system was adopted to observe the solidification front of each transformation. It showed that for residual liquid solidification, the solidification front velocity is the same magnitude as that for eutectic transformation, but is an order of magnitude larger than for metastable eutectic transformation, which confirms the reaction as L_r → Ni/Ni₃B; it also showed that this velocity decreases with increasing ΔT _r, which can be explained by reduction of the residual liquid fraction and decrease of Ni₂₃B₆ decomposition rate.     

Effect of the overheating of the gallium melt on its supercooling during solidification

The effect of overheating ΔT _L ⁺ of the gallium melt on its supercooling ΔT _L ^? during solidification is studied by cyclic thermographic analysis. The obtained data on ΔT _L ^? are used to calculate the thermodynamic and kinetic characteristics of gallium solidification.     

Metastable Phase Formation and Its Transformation in Highly Undercooled Ni75B25 Alloy

Ni₇₅B₂₅ alloy was solidified at various undercooling. The formation and subsequent transformation of metastable Ni₂₃B₆ phase were clearly identified. If undercooling prior to nucleation is less than a critical value of 240 K (240 °C), the alloy solidifies completely into Ni₃B phase. At larger undercooling, metastable Ni₂₃B₆ phase primarily forms in the melt but then is decomposed into α-Ni and Ni₃B through a eutectoid reaction. The decomposition simultaneously triggers the rapid solidification of residual liquid, due to which a second temperature recalescence occurs. The α-Ni/Ni₃B eutectoid is partially remelted if temperature exceeds the eutectic temperature during the second recalescence. Then, residual Ni₃B grows into coarse round grains while the remaining liquid re-solidifies into α-Ni/Ni₃B eutectic structure in the remelted region. In the case that the eutectic temperature is not reached, the eutectoid product with dot α-Ni distributing in Ni₃B matrix is retained in the solidification structure. A longer delay time between the two temperature recalescence events means less residual liquid, lower recalescence temperature and thus depressed remelting. The formation competition between Ni₃B and Ni₂₃B₆ phases in the alloy melt is nucleation controlled. The heterogeneous site in Ni₇₅B₂₅ alloy melt is a better nucleation substrate for Ni₂₃B₆ phase than for Ni₃B phase.

Graphical abstract

     

Effect of Thermal Aging on Ductile-Brittle Transition Temperature of Modified 9Cr-1Mo Steel Evaluated with Reference Temperature Approach Under Dynamic Loading Condition

The effect of thermal aging on the ductile-brittle transition behavior has been assessed for a modified 9Cr-1Mo steel (P91) using the reference temperature approach under dynamic loading condition (T ₀ ^dy ). The steel in normalized and tempered (NT) condition and in different levels of subsequent cold work (CW) was subjected to thermal aging at temperatures of 873 K and 923 K (600 °C and 650 °C) for 5000 and 10,000 hours. For the NT and all the cold work conditions of the starting material, a drastic increase in T ₀ ^dy has been noticed after aging at 923 K (650 °C) for 10,000 h. A moderate increase was observed for the NT steel aged at 873 K (600 °C) for 5000 hours and for the 10 pct CW steel aged at 873 K (600 °C) for 10,000 h. A detailed transmission electron microscope (TEM) study of the embrittled materials aged at 923 K (650 °C)/10,000 hours and 873 K (600 °C)/10,000 hours has indicated presence of hexagonal Laves phase of Fe₂(Mo,Nb) type with different size and spatial distributions. The increase in the T ₀ ^dy is attributed to the embrittling effect of a network of Laves phase precipitates along the grain boundaries.     

Influence of Phosphorus on the Nucleation of Eutectic Silicon in Al-Si Alloys

The role of phosphorus (P) in the heterogeneous nucleation of eutectic silicon (Si) and the evolution of eutectic grains in hypoeutectic aluminum-silicon alloys were investigated. Systematic additions of P in the range of 0.5 to 20 ppm to Al-7 wt pct Si alloys of different purities have shown that the morphology of the eutectic Si changes from a fine plate- to a coarse flake-like structure. The growth of eutectic grains was investigated by interrupting the eutectic reaction by quenching experiments. Moreover, the macroscopic growth mode of the eutectic grains was characterized by electron backscatter diffraction. An increase in P concentration from 2 to 3 ppm resulted in a transition of the macroscopic growth mode of the Al-Si eutectic in high purity alloys from growth with a planar front with a strong dependence of the thermal gradient, to nucleation in the vicinity of the primary Al dendrites and subsequent growth of distinct eutectic grains. It is suggested that AlP particles are the key impurities acting as potential nucleation sites for eutectic Si. This is further substantiated as with increasing P concentration nucleation and growth of the Al-Si occurred at higher temperatures close the equilibrium Al-Si eutectic solidification temperature at 850 K (577 °C). In addition, the recalescence undercooling ΔT _R,eu was reduced from 4.5 K (0.5 ppm P) to 1.5 K (20 ppm P) in high purity alloys. This was accompanied by a drastic increase of the nucleation rate of the eutectic grains.     

Phase Selection and Microstructure Evolution in Nonequilibrium Solidification of Fe40Ni40B20 Alloy

Phase selection and microstructure evolution in nonequilibrium solidification of ternary eutectic Fe₄₀Ni₄₀B₂₀ alloy have been studied. It is shown that γ-(Fe, Ni) and (Fe, Ni)₃B prevail in all the as-solidified samples. No metastable phase has been found in the deeply undercooled samples. This is explained as resulting from the size effect of undercooled solidification. At small and medium undercoolings, the dendrite γ-(Fe, Ni) appears as the leading phase. This is ascribed to the existence of the skewed coupled growth zone in FeNiB alloy. With increasing undercooling, the amount of dendrites first increases and then decreases, accompanied by a transition from regular eutectic to anomalous eutectic. The formation mechanisms of the anomalous eutectics are discussed. Two kinds of microstructure refinement are found with increasing undercooling in a natural or water cooling condition. However, for melts with the same undercooling, the as-solidified microstructure refines first, and then coarsens with an increasing cooling rate. The experimental results show that the nanostructure eutectic cell has been obtained in the case of Ga-In alloy bath cooling with an initial melt undercooling of approximately 50 K (50 °C).     

Calorimetry Investigation of Phase Stability and Thermal Property in Ti-5 % Ta Alloy

An accurate measurement of enthalpy increment H _T–H _298.15 has been made for Ti-5 % Ta alloy in the temperature range of 463–1,257 K using drop calorimetry. This temperature interval covers the low temperature α + β two phase and also the α(hcp) → β(bcc) transformation domain (1,083 K ≤ T ≤ 1,183 K), in which the enthalpy versus temperature variation exhibited a clearly delineated inflection. The drop calorimetry data has been phenomenologically modelled to obtain the transformation enthalpy, Δ°H _tr ^α→β as 66 J g^?1. Further, in the α → β diffusive transformation zone the transformation kinetics has been quantitatively modelled in terms of Kolmogorov–Johnson–Mehl–Avrami model of diffusion limited phase transformation, to obtain the effective activation energy as 284 ± 10 kJ mol^?1.     

Microstructural characteristics of Ni-Sb eutectic alloys under substantial undercooling and containerless solidification conditions

Both Ni-36 wt pct Sb and Ni-52.8 wt pct Sb eutectic alloys were highly undercooled and rapidly solidified with the glass-fluxing method and drop-tube technique. Bulk samples of Ni-36 pct Sb and Ni-52.8 pct Sb eutectic alloys were undercooled by up to 225 K (0.16 T _E ) and 218 K (0.16 T _E ), respectively, with the glass-fluxing method. A transition from lamellar eutectic to anomalous eutectic was revealed beyond a critical undercooling ΔT ₁*, which was complete at an undercooling of ΔT ₂*. For Ni-36 pct Sb, ΔT ₁*≈60 K and ΔT ₂*≈218 K; for Ni-52.8 pct Sb, ΔT ₁*≈40 K and ΔT ₂*≈139 K. Under a drop-tube containerless solidification condition, the eutectic microstructures of these two eutectic alloys also exhibit such a “lamellar eutectic-anomalous eutectic” morphology transition. Meanwhile, a kind of spherical anomalous eutectic grain was found in a Ni-36 pct Sb eutectic alloy processed by the drop-tube technique, which was ascribed to the good spatial symmetry of the temperature field and concentration field caused by a reduced gravity condition during free fall. During the rapid solidification of a Ni-52.8 pct Sb eutectic alloy, surface nucleation dominates the nucleation event, even when the undercooling is relatively large. Theoretical calculations on the basis of the current eutectic growth and dendritic growth models reveal that γ-Ni₅Sb₂ dendritic growth displaces eutectic growth at large undercoolings in these two eutectic alloys. The tendency of independent nucleation of the two eutectic phases and their cooperative dendrite growth are responsible for the lamellar eutectic-anomalous eutectic microstructural transition.     

Thermodynamics of the system NaCl-AlCl3

Heat capacities of melts were measured in the range 400 to 1100 K and 0.48 < N_AlCl3 < 0.62, the results being expressed by C_p = 40.96 – 0.0295T + 2.01 × 10^?5 T ² J K^?1 g·atom^?1 i.e., AlCl₃ contains 4 atoms, and so forth). This equation was used in interpreting literature vapor pressure data. Measurements were made of the emf of the concentration cell $$AL\left| {_{AlCl_3 }^{NACl(sat)} } \right.\left| {_{(Na^ + )}^{Pyrex} } \right.\left| {_{AlCl_3 }^{NACl(sat)} } \right.\left| {_{AlCl_3 }^{NACl} } \right.\left| {AL} \right. $$ at temperatures 473 to 623 K, and the results were correlated with the vapor pressure data to yield activities of NaCl and AlCl₃. Measurements with a sodium electrode confirmed the accepted values for the free energy of formation of A1C1₃ within about 1.5 kJ mol^?1. The activities were used to analyze the phase diagram. Direct measurement of the eutectic temperature with a concentration-cell technique (which avoids supercooling) gave 386 K; the eutectic composition is 60.0 mol pct A1C1₃. The standard entropy of NaAlCl₄(s) is S _298.15 ^° = 199.1 J K^?1 mol^?1. The free energy for NaAlCl₄(l) = NaAlCl₄(g) is ΔG° = 82740 ?63.66T J mol^?1 at around 950 K.     

Thermodynamic properties of dilute solutions of oxygen in liquid Fe−Co and Fe−Ni systems

Ther modynamic properties of oxygen in liquid Fe?Co and Fe?Ni binary mixtures have been investigated by equilibration with appropriate mixtures of H₂ and H₂O. The results show that Henry's law is obeyed by dissolved oxygen at all the possible concentrations of oxygen in each binary mixture. The standard Gibbs energy of solution of oxygen ΔG _Q ^° has been presented as a function of temperature for various binary compositions. The variation of ΔG _Q ^° with composition at 1550°C for each system follows a theoretical correlation based on a new treatment of the first approximation to the regular solutions.     

Theory of eutectic growth under rapid solidification conditions

The Jackson-Hunt model of eutectic growth at small undercoolings is extended to large undercooling values which are commonly encountered under rapid solidification conditions. The parameters, λ²V and λΔT, are found to deviate from constant values at high velocities, and these deviations depend upon the nature of the metastable phase diagram below the eutectic temperature. A limiting velocity is predicted for the formation of a regular, coupled eutectic structure, and the reason for this limiting velocity is shown to be either the temperature dependent diffusion coefficient or the limit of undercooling.     

Microstructure of Precipitation Hardenable Powder Metallurgical Ni Alloys Containing 35 to 45 pct Cr and 3.5 to 6 pct Nb

Ni-based alloys with high Cr contents are not only known for their excellent high temperature and hot corrosion resistance, but are also known for poor mechanical properties and difficult workability. Powder metallurgical (PM) manufacturing of alloys may overcome several of the shortcomings encountered in materials manufacturing involving solidification. In the present work, six PM Ni-based alloys containing 35 to 45 wt pct Cr and 3.5 to 6 wt pct Nb were produced and compacted via hot isostatic pressing. Samples were heat treated for up to 1656 hours at either 923 K or 973 K (650 °C or 700 °C), and the microstructures and mechanical properties were quantified and compared to thermodynamic calculations. For the majority of the investigated alloys, the high Cr and Nb contents caused development of primary populations of globular α-Cr and δ (Ni₃Nb). Transmission electron microscopy of selected alloys confirmed the additional presence of metastable γ″ (Ni₃Nb). A co-dependent growth morphology was found, where the preferred growth direction of γ″, the {001} planes of γ-Ni, caused precipitates of both α-Cr and δ to appear in the form of mutually perpendicular oriented disks or plates. Solution heat treatment at 1373 K (1100 °C) followed by aging at 973 K (700 °C) produced a significant strength increase for all alloys, and an aged yield strength of 990 MPa combined with an elongation of 21 pct is documented for Ni 40 wt pct Cr 3.5 wt pct Nb.     

The diffusion of hydrogen in liquid Ni,Cu, Ag,and Sn

The rates of absorption of hydrogen in stagnant liquid Ni, Cu, Ag, and Sn have been measured using 1) an unsteady-state gas-liquid metal diffusion cell technique similar to that used by El-Tayeb and Parlee for iron and 2) a steady-state diffusion cell technique recently developed in this laboratory. The rates of absorption are considered to be controlled by diffusion in the liquid. On this basis the chemical diffusion coefficients of hydrogen (D _H) in liquid Ni, Cu, and Ag, calculated from the rate data, can be described by:D _H ^Ni =7.47×10^?3 exp(?8550±1114/RT) cm²/secD _H ^Cu =10.91×10^?3 exp(?2148±349/RT) cm²/secD _H ^Ag =4.54×10^?2 exp(?1359±207/RT) cm²/sec In the above equations, the uncertainty in the activation energy (Q _H) corresponds to the 90 pct confidence level. No reliable Arrhenius equation could be obtained forD _H ^Sn , but theD _H values in tin are greater than for the other three metals. The following interesting and possibly significant correlations are observed betweenD _H,Q _H, and the hydrogen solubility (S _H):D _H ^Ni <D _H ^Fe <D _H ^Cu <D _H ^Ag <D _H ^Sn , andQ _H ^Ni >Q _H ^Fe >Q _H ^Cu >Q _H ^Ag , andS _H ^Ni >S _H ^Fe >S _H ^Cu >S _H ^Ag >S _H ^Sn .     

Phase Equilibria,Microstructure, and High-Temperature Strength of TiC-Added Mo-Si-B Alloys

TiC was added to Mo-Si-B alloys using a conventional Ar arc-melting technique, and the phase equilibria, microstructure evolution, and high-temperature strength at 1673 K (1400 °C) were investigated. The primary phase changed to Mo solid solution (Mo_ss), Mo₅SiB₂ (T₂), or TiC depending on the composition. Following the primary phase solidification, a Mo_ss + TiC, Mo_ss + T₂, or Mo_ss + T₂ + TiC + Mo₂C eutectic reaction took place as the secondary solidification step. In some alloys, Mo_ss + T₂ + TiC and Mo_ss + T₂ + Mo₂C eutectic reactions were present as higher-order solidification steps. After annealing at 2073 K (1800 °C) for 24 hours, Mo_ss, T₂, TiC, and Mo₂C coexisted stably with microstructural coarsening. The coarsening rate was much faster in an alloy with no TiC dispersion, suggesting that TiC has a strong pinning effect on the grain boundary and interface migration. Compression tests conducted at 1673 K (1400 °C) revealed strength properties of almost all the alloys that were better than those of the Mo-Hf-C alloy (MHC). Alloy densities were 9 g/cm³ or less, which is lighter than pure Mo and MHC (≥10 g/cm³) and competitive with Ni-base superalloys. TiC-added Mo-Si-B alloys are promising candidates for ultrahigh-temperature materials beyond Ni-base superalloys.     

Effects of Undercooling and Cooling Rate on Peritectic Phase Crystallization Within Ni-Zr Alloy Melt

The liquid Ni-16.75 at. pct Zr peritectic alloy was substantially undercooled and containerlessly solidified by an electromagnetic levitator and a drop tube. The dependence of the peritectic solidification mode on undercooling was established based on the results of the solidified microstructures, crystal growth velocity, as well as X-ray diffraction patterns. Below a critical undercooling of 124 K, the primary Ni₇Zr₂ phase preferentially nucleates and grows from the undercooled liquid, which is followed by a peritectic reaction of Ni₇Zr₂+L → Ni₅Zr. The corresponding microstructure is composed of the Ni₇Zr₂ dendrites, peritectic Ni₅Zr phase, and inter-dendritic eutectic. Nevertheless, once the liquid undercooling exceeds the critical undercooling, the peritectic Ni₅Zr phase directly precipitates from this undercooled liquid. However, a negligible amount of residual Ni₇Zr₂ phase still appears in the microstructure, indicating that nucleation and growth of the Ni₇Zr₂ phase are not completely suppressed. The micromechanical property of the peritectic Ni₅Zr phase in terms of the Vickers microhardness is enhanced, which is ascribed to the transition of the peritectic solidification mode. To suppress the formation of the primary phase completely, this alloy was also containerlessly solidified in free fall experiments. Typical peritectic solidified microstructure forms in large droplets, while only the peritectic Ni₅Zr phase appears in smaller droplets, which gives an indication that the peritectic Ni₅Zr phase directly precipitates from the undercooled liquid by completely suppressing the growth of the primary Ni₇Zr₂ phase and the peritectic reaction due to the combined effects of the large undercooling and high cooling rate.     

Effects of Alloying Elements on the Thermal Stability and Corrosion Resistance of an Fe-based Metallic Glass with Low Glass Transition Temperature

The effects of alloying elements on the thermal stability, glass-forming ability (GFA), corrosion resistance, and magnetic and mechanical properties of a soft magnetic Fe₇₅P₁₀C₁₀B₅ metallic glass with a low glass transition temperature (T _g) of 723 K (450°C) were investigated. The addition of Mo, Ni, and Co significantly increased the stabilization of supercooled liquid, GFA, and corrosion resistance in the H₂SO₄ solution. The maximum critical diameter (d _c) of 4 mm for glass formation was obtained for the Fe₅₅Co₁₀Ni₅Mo₅P₁₀C₁₀B₅ alloy, which shows the largest supercooled liquid region (ΔT _x ) of 89 K (89 °C). The substitution of Cr for Mo further enhanced the corrosion resistance of the Fe₅₅Co₁₀Ni₅Mo₅P₁₀C₁₀B₅, while the ΔT _x and d _c decreased. The (Fe, Ni, Co)₇₀(Mo, Cr)₅P₁₀C₁₀B₅ bulk metallic glasses showed low T _g of 711 K to 735 K (438 °C to 462 °C), wide ΔT _x of 67 K to 89 K, high saturation magnetization of 0.79 to 0.93 T, low coercive force of 2.36 to 6.61 A m^?1, high compressive yield strength of 3271 to 3370 MPa, and plastic strain of 0.8 to 2.3 pct. In addition, the mechanism for enhancing stability of supercooled liquid was discussed in terms of the precipitated phases during crystallization.     

Thermodynamics of the sublimation of calcium molybdate

The sublimation of CaMoO_4(s) is studied by high-temperature mass spectrometry at 1530–1770 K. CaMoO_4(g) and MoO_3(g) molecules are found to be present in the vapor; their vapor pressure is determined. The pressure of the CaMoO_4(g) molecule vapor is determined to be logp = ? 19 685/T + 5.52. The heat of sublimation ΔH _{s, 0} ^o (CaMoO_4(s)) = 446 ± 40 kJ/mol has been determined using the third law of thermodynamics. The atomization energy of the CaMoO_4(g) molecules is calculated to be ΔH _{at, 0} ^o (CaMoO_4(g)) = 2910 ± 40 kJ/mol.     

Nonequilibrium Solidification Behavior of Co-Si Alloys Near the First Eutectic Point

Adopting a fluxing purification and cyclic superheating technique, Co-10 wt pct Si and Co-15 wt pct Si alloys had been undercooled to realize rapid solidification in this work. It was investigated that the solidification modes and microstructures of Co-Si alloys were deeply influenced by the undercooling of the melts. Both alloys solidified with a near-equilibrium mode in a low undercooling range; the peritectic reaction occurred between the primary phase and the remnant liquids, and it was followed by the eutectic reaction and eutectoid transformation. With the increase of undercooling, both alloys solidified with a nonequilibrium mode, and the peritectic reaction was restrained. As was analyzed, a metastable Co₃Si phase was found in Co-10 wt pct Si alloy when a critical undercooling was achieved.