Phase equilibria and solid state transformations in Nb-rich Nb–Ti–Al intermetallic alloys

The solidification pathways and phase equilibria at 1100, 900 and 700°C in seven Nb-rich alloys of the Nb–Ti–Al system were examined. The as-cast microstructures revealed that all alloys had undergone β solidification, extending the range of the β phase field further into the ternary system than previously reported. Changes in the atomic site occupancy preferences with alloy composition were examined for the B2 ordered β₀ phase through atom location by channeling-enhanced microanalysis (ALCHEMI). A β to δ massive-like transformation observed in cast material, was reproduced in continuously cooled homogenized samples. The formation of a new phase, θ, based on the I4₁/amd body centered tetragonal structure was observed below 1100°C. In addition, a metastable hP18 structure, produced through an ω-type transformation of the β₀ phase, was also observed.     

Phase equilibria in the Ti–Al binary system

New experimental results on the phase equilibria between the β-Ti (A2), α-Ti (A3), α₂-Ti₃Al (D0₁₉) and the γ-TiAl (L1₀) phases in the Ti–Al system using specimens with low levels of oxygen are presented. The results obtained on the α/γ and the α₂/γ equilibria are in good agreement with the previous experimental and calculated phase boundaries, while the ones obtained on the α/β equilibrium deviate significantly from the previously proposed phase diagram. It is confirmed that the β phase field extends to higher aluminum contents and that the width of the α+β two-phase region is very narrow, less than 1 at.% Al. The presence of the A2/B2 order–disorder transition in the β phase is also confirmed by a combination of differential scanning calorimetric (DSC) analysis and extrapolation of ordering phase boundaries from the Ti–Al–X (X=Cr, Fe) ternary systems. A thermodynamic analysis has been carried out taking into account the ordering configurations in the β-Ti (A2)/β₂-TiAl (B2), f.c.c.-Al (A1)/γ-TiAl (L1₀) and α-Ti (A3)/α₂-Ti₃Al (D0₁₉) equilibria. It is proposed that the anomalous α/β equilibrium is due to the A2/B2 ordering reaction.     

Phase decomposition of the γ phase in a Mn–30 at.% Cu alloy during aging

The phase decomposition process of γ phase in a Mn–30 at.% Cu alloy, when aged at 723 K from 2 to 50 h, is investigated with electrical resistivity and magnetic susceptibility measurement. In conjunction with the antiferro-magnetic transition of the Mn-rich regions during cooling to room temperature from the aging temperature, the temperature coefficient of electrical resistivity shows a continuous increase in a certain temperature range. The temperature where the coefficient has the maximum increasing rate is defined as the T_N temperature of the Mn-rich regions. It was found that the T_N temperature was 20–30 K higher than the concomitant f.c.c.–f.c.t. transformation temperature T_t, determined with the minima of Young’s modulus in the aged samples. The increment of temperature coefficient of electrical resistivity involved in the magnetic transition is used to estimate the changes of volume fraction for Mn-rich regions vs aging time. At the same time, the paramagnetic feature above the spin-freezing transition temperature for quenched Cu-rich alloys is summarized, and the Mn concentration in Cu-rich regions of aged samples is calculated. It should be noted that Mn and Cu-rich regions had already formed in the 2 h-aged Mn–30 at.% Cu sample, and longer aging further enriched Mn or Cu, while the volume fraction of Mn-rich regions decreased slightly with aging time. Electrical resistivity measurement sensitive to Mn-rich regions and the magnetic susceptibility measurement for Cu-rich regions have shown the compositional heterogeneity in decomposed phases. TEM observation confirms the interconnectivity of the two regions in the aged microstructure. All the results support the hypothesis that the decomposition of γ phase in Mn–Cu alloys proceeds in the spinodal manner.     

Phase separation kinetics in a Fe–Cr–Al alloy

The α–α′ phase separation kinetics in a commercial Fe–20 wt.% Cr–6 wt.% Al oxide dispersion-strengthened PM 2000? steel have been characterized with the complementary techniques atom probe tomography and thermoelectric power measurements during isothermal aging at 673, 708, and 748 K for times up to 3600 h. A progressive decrease in the Al content of the Cr-rich α′ phase was observed at 708 and 748 K with increasing time, but no partitioning was observed at 673 K. The variation in the volume fraction of the α′ phase well inside the coarsening regime, along with the Avrami exponent 1.2 and activation energy 264 kJ mol^?1, obtained after fitting the experimental results to an Austin–Rickett type equation, indicates that phase separation in PM 2000? is a transient coarsening process with overlapping nucleation, growth, and coarsening stages.     

Phase equilibria in Ti–Ni–Pt ternary system

Phase equilibria in Ti–Ni–Pt ternary system have been experimentally determined through diffusion triple technique combined with alloy samples approach. Assisted with electron probe microanalysis (EPMA) and X-ray diffraction (XRD) techniques, isothermal sections at 1073 and 1173 K of this system were constructed and existence of ternary phase Ti₂(Ni,Pt)₃ was confirmed. In addition, binary compounds Ti₃Pt₅ and TiPt_3– were found to be stable at 1073 and 1173 K, and remarkable ternary solubility in some binary compounds was detected, e.g., solubility of Pt in TiNi can be up to about 36% (molar fraction) at 1073 K and 40% (molar fraction) at 1173 K. Furthermore, a ternary invariant transition reaction TiNi₃+Ti₃Pt₅→Ti₂(Ni,Pt)₃+TiPt₃₊ at a temperature between 1073 and 1173 K was deduced.     

Phase equilibria in the Al–Mo–Si system

The ternary Al–Mo–Si phase diagram was investigated by a combination of optical microscopy, powder X-ray diffraction (XRD), differential thermal analysis (DTA), electron probe microanalysis (EPMA) and scanning electron microscopy (SEM). Ternary phase equilibria were investigated within two isothermal sections at 600 °C for the Mo-poor part and 1400 °C for the Mo-rich part of the phase diagram. The solubility ranges of several phases including MoSi₂ (C11_b) as well as Mo(Si,Al)₂ with C40 and C54 structure were determined. The binary high temperature phase Al₄Mo was found to be stabilized at 600 °C by addition of Si. DTA was used to identify 9 invariant reactions and thus constructing a ternary reaction scheme (Scheil diagram) in the whole composition range. A liquidus surface projection was constructed on basis of the reaction scheme in combination with data for primary crystallization from as-cast samples determined by SEM measurements.     

Phase equilibria in the system Al–Co–Si

The Al–Co–Si system was studied for three isothermal sections at 600 °C (equilibria with Si), 800 °C (alloys up to 50 at.% Co) and 900 °C (alloys with more than 50 at.% Co). A total number of seven ternary compounds were characterized in the ternary system and the homogeneity ranges of the various ternary solid solutions of binary Co–Al and Co–Si compounds were studied. X-ray powder diffraction and optical microscopy was used for initial sample characterization and electron probe microanalysis of the annealed samples was used to determine the phase compositions within the ternary system. Lattice parameters have been determined for all ternary compounds and the change of lattice parameters with the composition is given for the solid solution phases.     

The formation mechanism of the O phase in a Ti3Al–Nb alloy

It is reported that there are several different transformation mechanisms of the O phase in different heat treatment conditions in the Ti₃Al based alloys. However, very little work has been carried out on the α₂→O phase transformation in the Ti₃Al–Nb alloys of Nb amounts exceeding 12 at%. In this paper, the formation mechanism of the O phase in the Ti–24Al–14Nb–3V–0.5Mo (at%) alloy has been carried out by means of TEM and HRTEM. The results show that the O phase is directly derived from the primary equiaxed α₂ grains with a fine streak contrast, and exists in multivariant forms owing to its different orientations after the alloy is solution treated at 1000°C for 1 h followed by water quenching (WQ) and aged at 650°C for 24 h. The O plates in the primary equiaxed α₂ grains exist not only in the form of a single variant, but also in the form of fine α₂+O mixtures. The analysis indicates that the formation of the O phase is the result of a phase decomposition, that is the introduction of niobium as the preferred β stabilizer makes the supersaturation of niobium in the primary α₂ grains, and the α₂ phase containing Niobium separates into Niobium lean and Niobium rich regions through the Niobium diffusion: α₂→α₂(Nb-lean)+O(Nb-rich). Niobium rich regions transform to the ordered orthorhombic phase (O phase) with a lattice distortion and only a very small composition change. It appears, therefore, that the transformation involves nucleation, growth and coarsening of the O phase by a diffusion mechanism.     

Phase equilibria and structural investigations in the system Al–Fe–Si

The Al–Fe–Si system was studied for an isothermal section at 800 °C in the Al-rich part and at 900 °C in the Fe-rich part, and for half a dozen vertical sections at 27, 35, 40, 50 and 60 at.% Fe and 5 at.% Al. Optical microscopy and powder X-ray diffraction (XRD) was used for initial sample characterization, and Electron Probe Microanalysis (EPMA) and Scanning Electron Microscopy (SEM) of the annealed samples was used to determine the exact phase compositions. Thermal reactions were studied by Differential Thermal Analysis (DTA). Our experimental results are generally in good agreement with the most recent phase diagram versions of the system Al–Fe–Si. A new ternary high-temperature phase τ₁₂ (cF96, NiTi₂-type) with the composition Al₄₈Fe₃₆Si₁₆ was discovered and was structurally characterized by means of single-crystal and powder XRD. The variation of the lattice parameters of the triclinic phase τ₁ with the composition Al_2+xFe₃Si_3?x (?0.3 < x < 1.3) was studied in detail. For the binary phase FeSi₂ only small solubility of Al was found in the low-temperature modification LT-FeSi₂ (ζ_β) but significant solubility in the high-temperature modification HT-FeSi₂ (ζ_α) (8.5 at.% Al). It was found that the high-temperature modification of FeSi₂ is stabilized down to much lower temperature in the ternary, confirming earlier literature suggestions on this issue. DTA results in four selected vertical sections were compared with calculated sections based on a recent CALPHAD assessment. The deviations of liquidus values are significant suggesting the need for improvement of the thermodynamic models.     

High temperature phase equilibria near Ti–50 at% Al composition in Ti–Al system studied by directional solidification

High temperature phase diagram near the stoichiometric composition of TiAl has been established by the directional solidification and quenching technique. The quenched dendrite morphologies showed that the first solidified phase was the β phase in Ti–44, 46, 48 at% Al alloys and the α phase in Ti–50, 52 at% Al alloys. From the EDS analysis of the quenched dendrite tips and measurement of the temperature gradient directly recorded during directional solidification in Ti–(44–52 at%)Al alloys, the solid-liquid phase equilibria could be determined. The phase transformation temperatures were also confirmed by DTA. The phase equilibria established in this study agreed with the phase diagram that Okamoto proposed, while the β+γ two phase region, which Murray suggested, was not found near the TiAl composition. The lamellar orientation in TiAl alloys has been reported to be controlled in the growth direction in the presence of the primary β phase from a liquid. A composition in which the liquid phase was fully transformed to the β phase was selected, Ti–44 at% Al alloy, and directional solidification was performed at the growth rate of 45 mm/h. It was found that the lamellar orientation was aligned at nearly 0° and 45° to the growth direction. It is thought that the success in controlling the lamellar orientation is due to β solidification of the Ti–44 at% Al alloy at the beginning of liquid/solid transformation.     

Intermetallic phase transformations in Au–Al wire bonds

This paper describes the crystallochemical mechanisms that underpin the migration of nano-size alumina, intermetallic growth and phase transformations in Au–Al wire bonds during annealing from 175 °C to 250 °C by utilizing high-resolution transmission electron microscopy (HRTEM). Alumina, encapsulated within the Au–Al intermetallic compounds (IMCs), migrates towards the Au ball during annealing, with Au diffusion into the Al pad. The sequence of Au–Al IMC phase development during annealing was investigated. Initially, Au₈Al₃ appears as a third phase between the Au₄Al and AuAl₂ layers that form during bonding, and gradually becomes the dominant compound. Both AuAl₂ and Au₈Al₃ are transformed into the Au-rich alloyAu₄Al when Al is completely consumed, and this is the terminal product.     

Stress-induced phase transformation during superplastic deformation in two-phase Ti–Al–Fe alloy

Ti–5.5Al–1Fe alloys consisting of the h.c.p.-α phase and the b.c.c.-β phase were investigated for microstructural changes during superplastic deformation at temperatures from 1050 to 1200 K. Observed changes occurred in two steps: (1) agglomeration of the β phase to grain boundaries perpendicular to the tensile axis and (2) subsequent increase of the β volume fraction. The β volume fraction after failure was found to increase with increasing deformation temperature. The first step was considered to be induced by the gradient of traction force acting upon grain boundaries. The second step was considered to be induced by stress concentration at grain boundaries of the α phase where the β phase was depleted by agglomeration to the perpendicular boundaries. The phase equilibrium under stressed condition was calculated by increasing the Gibbs energy of the α phase by 500 J/mol relative to that of the β phase. An excellent quantitative agreement was found between calculated results and experimental results of the β volume fraction and the Fe composition in each phase. The present work indicates that the phase transformation accompanied by diffusion can be induced by application of stress of the order of 100 MPa. This new type of stress-induced phase transformation can decrease the β transus temperature by more than 100 K.     

Phase transformations and induced volume changes in a nitrided ternary Fe–3%Cr–0.345%C alloy

Phase transformations during nitriding of a ternary carbon iron-based alloy Fe–3%Cr–0.345%C were studied, aiming for a better understanding of residual stresses generation and evolution. The relationship between the precipitation of Cr₇C₃ carbides and CrN nitrides, the induced volume change and the mechanical properties were investigated at three distinct depths of the diffusion zone. The relaxation of residual stresses arose through phase transformations according to the diffusion of nitrogen but also of carbon.     

Liquid–solid equilibria in the quasicrystalline regions of the Al–Pd–Mn phase diagram

Phase equilibria were investigated in the Al–Pd–Mn phase diagram in the region where quasicrystals and approximant phases form. With respect to previous thermodynamic studies, the extents of the liquidus phase fields of several approximant phases are either established or precisely determined. In particular, compositional profiles across interfaces show the ternary character of the T(AlPdMn) and ξ′ phases which are close to the binary Al–Mn and Al–Pd limits respectively. It is pointed out that the relative stability of some of the phases involves very small energy differences leading to very long transformation times and the solidification of metastable phases.     

Phase transformations in Al–Cu thin films: precipitation and copper redistribution

The (micro-)structural changes occurring in thin Al–Cu films of about 500 nm thickness and containing up to 1 at% Cu have been investigated. In particular, the copper distribution and the precipitation behaviour have been studied in situ during thermal cycling between 323 and 773 K. After slow cooling, large second-phase particles are observed which are mostly located at grain boundary triple points; the shape and size depend on the copper concentration. The average distance between these particles is about 16 μm, which is larger than the average grain size of approximately 1 μm. No second-phase particles have been observed within the aluminium grains. After cooling, a relatively large amount of copper (about 0.2 at%) as compared with bulk Al–Cu (0.001 at%) is not contained in second-phase particles. Most likely, this copper has segregated at grain boundaries, interfaces and dislocations. The temperature at which Al₂Cu starts to form in the thin films is well below the copper solvus for bulk material.     

Coarsening mechanisms in a dendritic Al–10% Cu alloy

Coarsening of a dendritic Al–10 wt.% Cu alloy at 570 °C was investigated by fast in situ X-ray tomography. The variation of the specific solid–liquid interface area as a function of time was found to follow a power-law relation with an exponent close to ?1/4. Three coarsening mechanisms operate in the alloy: (i) melting of small dendrite arms to the benefit of the adjacent arms (small arm melting), similar to Ostwald ripening; (ii) gradual movement of the base of the interdendritic grooves towards the tips (interdendritic groove advancement); (iii) coalescence of dendrites near the tips leading to the entrapment of liquid tubes or droplets (coalescence and groove advancement). The coarsening models proposed in the literature do not adequately resemble or predict the behaviour observed in the experiments. New models were developed for the first two coarsening mechanisms and predict the coarsening rate with very good agreement.     

On the ω phase formation in Cr–Al and Ti–Al–Cr alloys

The interaction between Al and the transition metals Ti and Cr on the stability of the ω phase in metastable β-based structures was studied. Alloys were quenched from the melt to retain at room temperature a metastable β phase (B2 structure), which is stable at high temperatures. The structural study of the ω phase was carried out by correlating the deviation of ω structure from the ideal ω phase to the compositions of the parent β phase. Deviation of ω structures from the ideal one was related to the electron concentration of the parent β phase. A diffuse ω structure is reported in the Cr₂Al phase (C11_b structure) for the first time. The results are consistent with our previous suggestions that Al stabilises the ω phase in transition metals by lowering the spatial conduction electron concentration in the parent β phase and by enhancing p–d hybridisation of valence electrons. In the ternary Ti–Al–Cr alloys, prolonged annealing of the Ti–30Al–10Cr and Ti–20Al–10Cr alloys at 450°C led to the formation of two types of ordered crystalline ω structure.