Phase equilibria and mechanical properties of the Ir–W–Al system

Phase equilibria in the Ir–W, Ir–Al and Ir–W–Al systems at temperatures between 1100 °C and 1600 °C were experimentally investigated using diffusion couples and two- or three-phase alloys, and the mechanical properties of γ′ (L1₂) strengthened Ir–W–Al alloys were examined by hardness and compression tests at room and elevated temperatures. The phase boundaries between the γ(A1)/ε′(D0₁₉), ε′/ε(A3) and ε/ε″(B19) in the Ir–W system at 1400 °C–1600 °C and those between the γ/β(B2) and β/Al_2.7Ir in the Ir–Al system at 1100 °C–1400 °C were determined. The phase diagrams in the Ir-rich corner of the Ir–W–Al ternary system at 1300 °C and 1400 °C were also determined. The existence of the γ′ phase of the Ir₃(W,Al) ternary compound was confirmed, and this system was found to consist of the γ, γ′, ε, ε′ and β phases in the Ir-rich portion. It was also found from hardness and compression tests up to 1200 °C that Ir–Al–W alloys having the γ + γ′ structure with a small lattice misfit show high hardness and strength at room and high temperatures.     

Effects of tantalum on the partitioning of tungsten between the γ- and γ′-phases in nickel-based superalloys: Linking experimental and computational approaches

Atom probe tomography (APT) and first-principles calculations are implemented to study the partitioning of W to the γ (face-centered cubic)- and γ′ (L1₂)-phases in Ni-based alloys. APT observations indicate that whereas W partitions preferentially to the γ′-phase in a ternary Ni–Al–W alloy, its partitioning behavior is reversed in favor of the γ-phase in multi-component alloys. Furthermore, the degree of W-partitioning to the γ′-phase decreases with the addition of Ta to a Ni–Al–Cr–W alloy, a trend which is consistent with Thermo-Calc simulations. First-principles calculations of the substitutional formation energies of W and Ta at 0 K predict that both elements prefer energetically sharing the Al-sublattice sites of the γ′-phase, whereas Ta has a larger tendency to partition to the γ′-phase than does W. This implies that Ta displaces W from the γ′-phase into the γ-phase in multi-component Ni-based alloys.     

Mechanical properties and lattice misfit of γ/γ′ strengthened Co-base superalloys in the Co–W–Al–Ti quaternary system

A continuous γ/γ′ two-phase field has been identified extending between the ternary Co–Al–W system to the binary Co–Ti system. The lattice misfits of two phase γ/γ′ alloys from the Co–Al–W–Ti quaternary system were measured by X-ray diffraction and found to be positive and vary linearly with composition. Differential scanning calorimetry measurements showed that the solidus and liquidus temperatures decrease from the W and Al rich end to the Ti rich end, whilst the γ′ solvus temperature increases. Long term heat treatments identified the occurrence of discontinuous precipitation at the grain boundaries in many of the alloys studied. The high temperature strength and creep resistance of the quaternary alloys in the intermediate composition range surpassed those of the binary and ternary alloys.     

Effects of rhenium addition on the temporal evolution of the nanostructure and chemistry of a model Ni–Cr–Al superalloy. I: Experimental observations

The temporal evolution of the nanostructure and chemistry of a model Ni–8.5 at.% Cr–10 at.% Al alloy, with the addition of 2 at.% Re, aged at 1073 K from 0.25 to 264 h, was studied. Transmission electron microscopy and atom-probe tomography were used to measure the number density and mean radius of the γ′ (L1₂ structure)-precipitates and the chemistry of the γ′-precipitates and the γ (face-centered cubic)-matrix, including the partitioning behavior of all alloying elements between the γ- and γ′-phases and the segregation behavior at γ/γ′ interfaces. The precipitates remained spheroidal for an aging time of up to 264 h and, unlike commercial nickel-based superalloys containing Re, there was not confined (nonmonotonic) Re segregation at the γ/γ′ interfaces.     

Microstructure,oxidation resistance and high-temperature strength of γ′ hardened Pt-base alloys

Starting from the base composition with 12 at.% Al, 6 at.% Cr, 5 at.% Ni and Pt balance, precipitation hardened Pt–Al–Cr–Ni alloys with additions of 2 at.% Mo, Re, Ru and W, respectively, were investigated. After homogenization heat treatment and air cooling, all five-component alloys show a bimodal distribution of γ′ precipitates. Along with a fraction of fine γ′ precipitates embedded in a Pt-rich matrix, some coarse primary γ′ particles are observed. Mo, Re and W additions increase strength above 1000 °C, whereas Ru has no beneficial effect on strength. W increases the γ′ volume fraction most effectively, however, the oxidation resistance is worsened dramatically by W additions. The Re-containing alloy shows the best resistance against γ′ growth and coarsening during long-term ageing.     

Impact of replacement of Re by W on dislocation slip mediated creeps of γ′-Ni3Al phases

The anomalous flow behavior of γ′-Ni₃Al phases at high temperature is closely related to the cross-slip of 1/2〈110〉{111} super-partial dislocations. Generalized stacking fault energy curves (i.e., Γ-surfaces) along the lowest energy path can provide a great deal of information on the nucleation and movement of dislocations. With the first-principles calculation, the interplay between Re and W, Mo, Ta, Ti doped at preferential sites and their synergetic influence on Γ-surfaces and ideal shear strength (τ_max) in γ′-Ni₃Al phases are investigated. Similar to single Re-addition, the Suzuki segregation of W at stacking faults is demonstrated to enable to impede the movement of 1/6〈112〉{111} Shockley partial dislocations and promote the cross-slip of 1/2〈110〉{111} super-partial dislocations. With the replacement of a part of Re by W, a decreased indicates that the anomalous flow behavior of γ′ phases at high temperature is not as excellent as the double Re-addition, but an increased τ_max means that the creep rupture strength of Ni-based single crystal superalloys can be benefited from this replacement to some extent, especially in the co-segregation of Re and W at Al−Al sites. As the interaction between X1_Al and X2_Al point defects is characterized by an correlation energy function , it is found that both strong attraction and strong repulsion are unfavarable for the improvement of yield strengths of γ′ phase.     

Lattice-parameter misfits between the γ and γ′ phases in single crystals of nickel superalloys

X-ray diffractometry has been used to study the transformation of the profiles of X-ray diffraction lines (222), (004), (003) and to determine the values of the lattice misfit between the γ and γ′ phases (γ/γ′ misfit) for single crystals of nickel superalloys ZhS6U, ZhS30, ZhS32, VZhM1, and VZhM4 in the as-cast state and after heat treatment. It has been established that with an increase in the γ/γ′ misfit there increase tetragonal distortions of the fcc lattice of the γ solid solution. For the single crystals of VZhM4 alloyed with rhenium and ruthenium, splitting of the superlattice reflection of the strengthening γ′ phase has been revealed. The structural regularities revealed testify to qualitative changes in the factors that govern the redistribution of refractory alloying elements between the lattices of the γ and γ′ phases, for example, of Mo in the presence of Re and Ru.     

Thermodynamic stability of Co–Al–W L12 γ′

Co-based superalloys in the Co–Al–W system exhibit coherent L1₂ Co₃(Al,W) γ′ precipitates in an face-centered cubic Co γ matrix, analogous to Ni₃Al in Ni-based systems. Unlike Ni₃Al, however, experimental observations of Co₃(Al,W) suggest that it is not a stable phase at 1173 K. Here, we perform an extensive series of density functional theory (DFT) calculations of the γ′ Co₃(Al,W) phase stability, including point defect energetics and finite-temperature contributions. We first confirm and extend previous DFT calculations of the metastability of L1₂ Co₃(Al_0.5W_0.5) γ′ at 0 K with respect to hexagonal close-packed Co, B2 CoAl and D0₁₉ Co₃W using the special quasi-random structure (SQS) approach to describe the Al/W solid solution, employing several exchange/correlation functionals, structures with varying degrees of disorder, and newly developed larger SQSs. We expand the validity of this conclusion by considering the formation of antisite and vacancy point defects, predicting defect formation energies similar in magnitude to Ni₃Al. However, in contrast to the Ni₃Al system, we find that substituting Co on Al sites is thermodynamically favorable at 0 K, consistent with experimental observation of Co excess and Al deficiency in γ′ with respect to the Co₃(Al_0.5W_0.5) composition. Lastly, we consider vibrational, electronic and magnetic contributions to the free energy, finding that they promote the stability of γ′, making the phase thermodynamically competitive with the convex hull at elevated temperature. Surprisingly, this is due to the relatively small finite-temperature contributions of one of the γ′ decomposition products, B2 CoAl, effectively destabilizing the Co, CoAl and Co₃W three-phase mixture, thus stabilizing the γ′ phase.     

Effects of rhenium addition on the temporal evolution of the nanostructure and chemistry of a model Ni–Cr–Al superalloy. II: Analysis of the coarsening behavior

The temporal evolution of the nanostructure and chemistry of a model Ni–8.5 at.% Cr–10 at.% Al alloy with the addition of 2 at.% Re was studied using transmission electron microscopy and atom-probe tomography in order to measure the number density and mean radius of the γ′ (L1₂) precipitates and the chemistry of the γ′-precipitates and the γ (fcc)-matrix. In this article, the coarsening behavior of the γ′-precipitates is discussed in detail and compared with the Umantsev–Olson model for multi-component alloys. In addition, the experimental results are evaluated with PrecipiCalc™ simulations. The results show that the diffusivities of the solute elements play a major role in the coarsening behavior of the γ′-precipitates and that the addition of Re retards the coarsening kinetics and stabilizes the spheroidal morphology of the precipitates by reducing the interfacial energy.     

Site preference of transition-metal elements in B2 NiAl: A comprehensive study

First-principles supercell calculations based on density functional theory were performed to study the T = 0 K site preference of 3d (Ti–Cu), 4d (Zr–Ag) and 5d (Hf–Au) transition-metal elements in B2 NiAl. By adopting a statistical-mechanical Wagner–Schottky model within the canonical ensemble, the effects of finite temperature on site preference were further considered. The calculations showed that, at all alloy compositions and temperatures, Co, Tc, Ru, Rh, Re, Os, Ir and Pt have a consistent preference for the Ni sublattice, while Ti, Zr, Nb, Hf and Ta have a consistent preference for the Al sublattice. In contrast, the site preference of V, Cr, Mn, Fe, Cu, Mo, Pd, Ag, W and Au was found to depend on both composition and temperature. The present calculated results compare favorably with existing theoretical and experimental studies in the literature.     

Partition behavior of alloying elements and phase transformation temperatures in Co–Al–W-base quaternary systems

The phase equilibria among γ (A1), γ′ (L1₂), χ (D0₁₉), β (B2) and μ (D8₅) phases and the γ′ solvus and γ solidus temperatures were investigated in the Co–Al–W-based quaternary systems with alloying elements of Ti, V, Nb, Ta, Cr, Mo, Mn, Fe, Ni, Si, Zr, Hf, Ru and Ir by electron probe microanalysis (EPMA) using multiphase alloys and by differential scanning calorimetry (DSC). It was found that Ta, Nb, Ti, V, Mo and W are partitioned to the γ′ or χ phase rather than to the γ phase, while Cr, Mn and Fe tend to be distributed to the γ phase. The correlation between the partition coefficient of alloying elements between γ/γ′, γ/χ and γ/β phases and ab initio formation energy of Co₃X (L1₂), Co₃X (D0₁₉) and CoX (B2) was respectively obtained. It was also found that the γ′ solvus temperature increases by the addition of the γ′ former elements such as Ta, Nb and Ti, which decreases the γ solidus temperature.     

Performance of Bond Coats Modified by Platinum Group Metals for Applications in Thermal Barrier Coatings

We have investigated the partial replacement of Pt with other less expensive Pt group metals on the properties of γ′ + γ bond coats used in thermal barrier coatings (TBCs) deposited on a nickel-base superalloy. The microstructure, thermal stability, oxidation behavior and performance in TBC systems of bond coats synthesized with Pt + Ru, Pt + Ir and Pt + Rh are compared with those of a reference bond coat synthesized with Pt. Yttria-stabilized zirconia has been employed as top coat in all coating systems. It is shown that at high temperatures all bond coats are degraded by interdiffusion and oxidation, however, with different kinetics. The lifetime of each TBC system is found to be limited by the cohesion between the thermally grown oxide and underlying bond coat. Differences in the behavior of various bond coats are correlated with their properties. Among the three Pt group metals investigated, the properties of the Pt + Ru bond coat are shown to closely approach those of the Pt bond coat. It is concluded that Ru with much lower cost presents a potential candidate for reducing the consumption of Pt.     

Cyclic oxidation of high temperature coatings on new γ′-strengthened cobalt-based alloys

An emerging class of cobalt-based γ′-strengthened alloys promises higher temperature capabilities compared to current Ni-base superalloys commonly used in aerospace and power generation applications. As with Ni-base alloys, high temperature coatings that enhance environmental resistance are desirable. Single crystal samples of Co–9.2Al–9.0W and Co–7.8Al–7.8W–4.5Cr–2.0Ta (at.%) were coated with vapour phase nickel aluminide and MCrAlY. Samples were subjected to cyclic oxidation at 1100 °C with 300–450 1-h cycles. Compared to NiAl-based coatings, the MCrAlY coatings exhibited superior adherence and an interdiffusion zone free of detrimental intermetallic phases. Evolution of microstructure during cycling is discussed with reference to the available thermodynamic data.     

The isotropic shear modulus of multicomponent Fe-base solid solutions

A critical analysis of the available experimental data for the effect of alloying elements on the isotropic shear modulus of bcc (body-centered cube) Fe–X (X=Al, Be, C, Co, Cr, Ge, Ir, Mn, Ni, Pt, Re, Rh, Ru, Si and V) solid solutions is carried out. The total effect of a solute on the shear modulus is decomposed into two contributions: the electronic (or chemical) and the volumetric. A systematic trend of the electronic contribution is demonstrated as a function of electron-to-atom (e/a) ratio and the ground-state electronic configuration of the solute atom. Based on the demonstrated trend, we predict the chemical contribution of the shear modulus of Cu, Mo, N, Nb, Ti and W in ferromagnetic α-Fe (bcc), and that of Ti and V in paramagnetic γ-Fe [face-centered cube (fcc)]. These along with the corresponding volumetric contributions enable us to predict the total effect of a solute on the shear modulus in α-Fe and γ-Fe. In the case of γ-Fe, we derive the chemical and volumetric contributions of Ni and Pt from the experimental shear modulus data of paramagnetic Fe–Ni and Fe–Pt alloys while those of C, Co, Cr, Mn, Mo, N and Si are derived from the shear modulus of paramagnetic Fe–Ni–X alloys. In the case of Al, Be, Cu, Ge, Ir, Nb, Re, Rh , Ru and W, the total effect on the shear modulus is calculated by assuming that the electronic contribution to the shear modulus in γ-Fe is the same as in α-Fe. To calculate the isotropic shear modulus of multicomponent bcc and fcc solid solutions, we propose linear superposition laws. The proposed relationships are validated using the experimental data of a large number of multicomponent alloys having austenitic, ferritic, and lath martensitic microstructures. It is demonstrated that for all three microstructures, in most cases the shear modulus can be predicted with an accuracy of ±3% in multicomponent solid solutions. It is also found that the high dislocation density in lath martensite accounts for a decrease in shear modulus by about 5% compared to the ferritic counterpart. We also demonstrate that the temperature dependence of shear modulus in multicomponent bcc and fcc solid solutions is similar to that of pure α- and γ-Fe, respectively, for up to about 800 K.     

Silver segregation to θ′ (Al2Cu)–Al interfaces in Al–Cu–Ag alloys

θ′ (Al₂Cu) precipitates in Al–Cu–Ag alloys were examined using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The precipitates nucleated on dislocation loops on which assemblies of γ′ (AlAg₂) precipitates were present. These dislocation loops were enriched in silver prior to θ′ precipitation. Coherent, planar interfaces between the aluminium matrix and θ′ precipitates were decorated by a layer of silver two atomic layers in thickness. It is proposed that this layer lowers the chemical component of the Al–θ′ interfacial energy. The lateral growth of the θ′ precipitates was accompanied by the extension of this silver bilayer, resulting in the loss of silver from neighbouring γ′ precipitates and contributing to the deterioration of the γ′ precipitate assemblies.     

Alloying effects in polycrystalline γ′ strengthened Co–Al–W base alloys

A polycrystalline hot working ingot metallurgy processing route for γ/γ^′ Co–Al–W superalloys has been developed. Based on Co–7Al–7W (at%), substitutions of Mo, V, Ti, Ta, Ni, Si, Fe and Cr were examined. The γ^′ solvus was found to follow the same trends as those exhibited by alloys with higher γ^′ fractions considered by other investigators. Excessive Cr additions were found to lead to discontinuous coarsening and eventually, the loss of the γ^′ phase from the microstructures observed. Ni additions were examined, with some success, and found to restore the γ′ phase and raise the solvus temperature. It was found that the addition of 13 at.% Cr improved the oxidation resistance at 800 °C by over 40 times.     

Partitioning and site occupancy of Ta and Mo in Co-base γ/γ′ alloys studied by atom probe tomography

The detailed understanding of solute partitioning and site occupancies of these solutes within the ordered γ′ (L1₂) precipitates holds a key role in the development of cobalt-base γ/γ′ alloys with optimized properties. The present atom probe tomography study utilizes both structural and compositional information to determine the partitioning behavior of transition elements like Ta and Mo between γ matrix and γ′ precipitates and their site occupancy within the γ′ phase. The addition of Ta, which enhances the formation of γ′, to a ternary Co–Al–W alloy with stoichiometric Co₃(Al,W) precipitates, results in the substitution of only the W in the γ′ precipitates to form Co₃(Al, W, Ta) precipitates. Interestingly, Mo, typically considered a γ solid solution strengthener in nickel-base alloys, also partitions strongly to γ′ precipitates when added to the Co–Al–W alloy and displaces only the W atoms. The experimentally observed equal atomic substitution of W by both Ta and Mo, without any change in the Al content within the γ′ precipitates, gives insights into the energetics of relative site substitutions in this ordered compound.     

First-principles study of site occupancy of dilute 3d, 4d and 5d transition metal solutes in L10 TiAl

Using a statistical-mechanical Wagner–Schottky model parametrized by first-principles density-functional (DFT-GGA) calculations on 32-atom supercells, we predict the lattice site occupancy of 3d (Ti–Cu), 4d (Zr–Ag) and 5d (Hf–Au) transition-metal elements in L1₀ TiAl intermetallic compound as a function of both alloy composition and temperature. The effects of local atomic relaxations, anisotropic lattice distortions, as well as magnetism on point defect energetics are fully taken into account. Our calculations show that, at all alloy compositions and temperatures, Zr and Hf consistently show a preference for the Ti sublattice, while Co, Ru, Rh, Pd, Ag, Re, Os, Ir, Pt and Au consistently show a preference for the Al sublattice. In contrast, the site preference of V, Cr, Mn, Fe, Ni, Cu, Nb, Mo, Tc, Ta and W strongly depend on both alloy stoichiometry and temperature. Our calculated results compare favorably with the existing theoretical and experimental studies in the literature.