Determination of the isothermal sections of the Al-Ni-Si ternary system at 750 °C and 850 °C

The phase equilibria of the Al-Ni-Si ternary system at 850 °C and 750 °C have been investigated using scanning electron microscopy (SEM) and electron-probe microanalysis (EPMA). Isothermal sections at 850 °C and 750 °C were constructed based on experimental data from 53 alloys heat treated at 850 °C for 1200 hours and at 750 °C for 1440 hours, respectively. The phase equilibria among the following intermetallics and solid-solution phases are described: Ll₂-Ni₃(Al,Si), B2-NiAl, Ni₅Si₂, δ-Ni₂Si, ϑ-Ni₂Si(τ ₄), Ni₃Si₂, NiSi, NiSi₂, Ni₂Al₃, NiAl₃, Ni₂AlSi(τ ₂), Ni₃Al₆Si(τ ₃), Ni₁₆AlSi₉(τ ₅), the fcc solid solution, and the diamond (Si) phase. In addition, a phase, temporarily designated as Ni₅(Al,Si)₃(τ ₆), was observed for the first time at both 750 °C and 850 °C. This phase is probably the stabilization of Ni₅Al₃ by Si to higher temperatures than the binary Ni₅Al₃, which is only stable at <∼700 °C.     

Thermodynamic activities and phase boundaries for the alloys of the solid solution of Co in Ni3Al

The vaporization of the alloy samples of the compositions (Ni₃Al)_1-x Co _x (x = 0, 0.03, 0.06, 0.09, 0.12, or 0.15) was investigated at temperatures between 1326 to 1581 K by the use of Knudsen effusion mass spectrometry in order to obtain thermodynamic data for the solid solution γ′ phase of the type Ni₃Al. The partial pressures of Al, Co, and Ni were determined over the samples investigated. Excess chemical potentials at a temperature of 1473 K resulted for the components in the γ′ solubility range. New results on the phase boundaries of the γ′ solubility lobe were obtained by the analysis of quenched alloy samples and from the mass spectrometric studies. The results obtained are discussed with respect to the solubility behavior of Co in the γ′ phase.     

Thermodynamic activities and partial enthalpies of mixing in the solid solution of Fe in Ni3Al

The vaporization of the alloy samples of the compositions (Ni₃Al)_1−x Fe _x (x=0, 0.01, 0.02, 0.03, 0.04, 0.06, 0.08) was investigated at temperatures between 1304 to 1698 K by the use of Knudsen effusion mass spectrometry in order to obtain thermodynamic data for the solid solutionγ′ phase of the type Ni₃Al. The partial pressures of Al, Fe, and Ni were determined over the samples investigated. Excess partial enthalpies, excess partial entropies, and excess chemical potentials at a temperature of 1473 K resulted for the components in theγ′ solubility range. New results on the phase boundaries of theγ′ solubility range were obtained by the analysis of quenched alloy samples and from the mass spectrometric studies. The results obtained are discussed with respect to the solubility behavior of Fe in theγ′ phase.     

Thermodynamic activities and phase boundaries for the alloys of the Ni3Al-Ni3Ti pseudobinary section in the Ni-Al-Ti system

The pseudobinary section Ni₃Al-Ni₃Ti of the ternary Ni-Al-Ti system has been investigated by ther-mal analysis and Knudsen effusion mass spectrometry. The solidus of the pseudobinary section and the thermodynamic activities of Ni and Al have been determined in the alloys Ni_0.75A1_0.25-xTi_x of the compositionsx = 0.00 to 0.21. Moreover, the thermodynamic activities of Ni and Ti in Ni₃Ti (x = 0.25) as well as the Gibbs energy of mixing of the Ni_0.75Ti_0.25 phase resulted. The ionization cross-sectional ratio Σ(Ni)/Σ(Ti) = 0.77 has been evaluated for the electron impact energy of 50 eV.     

Reaction Scheme and Liquidus Surface of the Ternary System Aluminum-Chromium-Titanium

The constitution of the ternary system Al-Cr-Ti is investigated over the entire composition range using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), differential thermal analysis (DTA) up to 1500 °C, and metallography. Solid-state phase equilibria at 900 °C are determined for alloys containing ≤75 at. pct aluminum and at 600 °C for alloys containing >75 at. pct Al. A reaction scheme linking these solid-state equilibria with the liquidus surface is presented. The liquidus surface for ≤50 at. pct aluminum is dominated by the primary crystallization field of bcc β(Ti,Cr,Al). In the region >50 at. pct Al, the ternary L1₂-type phase τ forms in a peritectic reaction p _max at 1393 °C from L + TiAl. Furthermore, with the addition of chromium, the binary peritectic L + α(Ti,Al) = TiAl changes into an eutectic L = α(Ti,Al) + TiAl. This eutectic trough descends monotonously through a series of transition reactions and ternary peritectics to end in the binary eutectic L = Cr₇Al₄₅ + (Al).     

Ordering reactions in Ni-Al-Mo-Ta and Ni-Al-Mo-W superalloys

The ordered structures formed in two experimental nickel base superalloys have been determined using selected area electron diffraction. Upon quenching from 1300 °C, the alloys contained ordered γ′ precipitates (L1₂ structure) and the matrix exhibited diffuse intensity at {1 1/2 0} positions, indicating the presence of short range order. The high refractory metal content of the alloys caused the D1a, DO₂₂, and Pt₂Mo prototype structures to form in the matrix following aging at 600, 700, and 800 °C. The detailed structural effects of the Ta and W quaternary additions are similar to those observed in Ni₃(Mo, Al), Ni₃(Mo,Ta), and Ni₃(Mo, W) ternary alloys. The decomposition products observed in the quaternary alloys studied can be explained by considering the partitioning of solutes between the γ′ and the matrix.     

Thermodynamic activities in the alloys of the Ti-Al-Nb system

The vaporization of the solid alloys of the Ti-Al-Nb system has been extensively studied, with emphasis on the α ₂-Ti₃Al, (α ₂-Ti₃Al+γ-TiAl), and γ-TiAl phase fields, by using Knudsen effusion mass spectrometry at temperatures between 1170 and 1635 K. Twenty-four alloy samples of different compositions, were investigated and their Ti and Al partial pressures were determined. The thermodynamic activities of Ti and Al, as well as partial enthalpies and entropies of mixing, were evaluated for the mean temperature of 1473 K. The data obtained are discussed with respect to their significance for high-temperature corrosion of titanium aluminides and the solubility behavior of Nb in the γ-TiAl phase.     

Isothermal section of the ternary Sn-Cu-Ni system and interfacial reactions in the Sn-Cu/Ni couples at 800 °C

The isothermal section of the Sn-Cu-Ni system at 800 °C has been experimentally determined. There is no ternary compound. A solid solution with a very wide compositional range, the γ phase is formed between the Ni₃Sn(H) phase and Cu₄Sn(H) phase; however, both of these two binary phases are not stable at 800 °C. The binary Ni₃Sn₂ phase also has extensive ternary solubility. The homogeneity ranges of both the γ and Ni₃Sn₂ phases are very large in parallel to the Cu-Ni side, but relatively narrow along the Sn direction. This phenomenon indicates that Cu and Ni are exchangeable in both phases. Three kinds of reaction couples, Sn-55 at. pct Cu/Ni, Sn-65 at. pct Cu/Ni, and Sn-75 at. pct Cu/Ni, were prepared and reacted at 800 °C for 5 to 20 minutes. The reaction paths are liquid/Ni₃Sn₂/γ/Ni₃Sn(L)/Ni for the Sn-55 at. pct Cu/Ni and Sn-65 at. pct Cu/Ni couples, and the reaction path is liquid/γ/Ni₃Sn(L)/Ni for the Sn-75 at. pct Ni couples.     

Phase equilibria of the ternary Al-Cu-Ni system and interfacial reactions of related systems at 800 °C

A series of Al-Cu-Ni alloys of various compositions were made and annealed at 800 °C. The equilibrium phases were studied by metallography, X-ray diffraction (XRD) analysis, and electron probe microanalysis. The isothermal section of the ternary Al-Cu-Ni system at 800 °C was then determined based on these experimental results and the available phase relationship knowledge of the three constituent binary systems. No ternary compound was found. All three phases, AlNi₃, AlNi, and Al₃Ni₂, have very high ternary solubility, especially the AlNi phase, which almost reaches the binary Al-Cu side. However, no continuous solid solution was formed between the AlNi phase and any of the binary Al-Cu phases. Interfacial reactions of Al/Ni, Al/Cu, Al-Cu/Ni, and Al-Ni/Cu at 800 °C were investigated by using reaction couple techniques. The results showed that Al₃Ni and Al₃Ni₂ phases were formed in the Al/Ni couples; β-AlCu₄, γ ₁-Al₄Cu₉, and ɛ ₂-Al₂Cu₃ phases were formed in the Al/Cu couples. As for the results in the Al-2 at. pct Ni/Cu, Al-5 at. pct Ni/Cu, and Al-2 at. pct Cu/Ni, Al-4.5 at. pct Cu/Ni, and Al-6 at. pct Cu/Ni were similar to those in the binary Al/Cu and Al/Ni couples, respectively. A different reaction path was found in the Al-7.5 at. pct Cu/Ni couples, and an AlNi solid solution layer was formed instead of the Al₃Ni and Al₃Ni₂ phases.     

INCOLOY 908, a low coefficient of expansion alloy for high-Strength cryogenic applications: Part I. Physical metallurgy

INCOLOY 908 is a low coefficient of thermal expansion (COE) iron-nickel base superalloy that was developed jointly by The Massachusetts Institute of Technology and the International Nickel Company for cryogenic service. The alloy is stable against phase transformation during prolonged thermal treatments and has a COE compatible with that of Nb₃Sn. These properties make the material ideal for use as a structural component in superconducting magnets using Nb₃Sn. The evolution of microstructure has been studied as a function of time at temperature over the temperature range of 650 °C to 900 °C for times between 50 and 200 hours. A detailed analysis of precipitated phases has been conducted using X-ray diffraction (XRD), transmission electron microscopy (TEM), and analytical scanning and scanning transmission electron microscopy (STEM) techniques. The primary strengthening phase has been found to be γ’, Ni₃(Al, Ti). INCOLOY 908 is stable against overaging, which is defined as the transformation of γ’ to η, Ni₃Ti, for times to 100 hours at temperatures up to 750 °C. Upon overaging, the strengthening phase transforms to η. A new phase,H _x, has been identified and characterized.     

X-ray diffraction study of the oxidation of Ni3(Al,Ti) alloys

Conclusions A study was made of the phase composition of the scale forming on Ni₃(Al + 15 at.% Ti) and Ni₃(Al + 5 at.%Ti) alloys during atmospheric oxidation at temperatures ranging from 600 to 1000°C. The scale was found to contain the oxides NiO, TiO₂ (rutile),-Al₂O₃, NiO · TiO₂, NiO · Al₂O₃, Ti₃O₅, and Ti₂O₃ together with Ni and a nickel base solid solution (Ni_ss). The character of the distribution of these phase constituents in successive scale layers after oxidation under various conditions is described. A correlation was found between the phase composition of the scale and certain kinetic oxidation characteristics of the alloys.Translated from Poroshkovaya Metallurgiya, No. 7 (151), pp. 70–74, July, 1975.     

Section of the isothermal tetrahedron of the Al-Cu-Mg-Zr phase diagram at 490°C

The phase equilibria in the Al-Cu-Mg-Zr system at 490°C have been studied for Al-rich alloys with 0.3% Zr and from 0 to 10% Cu or Mg. The (Al) solid solution is found to be in equilibrium with only binary θ(CuAl₂) and ZrAl₃ and ternary S (CuMgAl₂) phases of the ternary Al-Cu-Mg system. The section of the isothermal tetrahedron of the Al-Cu-Mg-Zr phase diagram at 490°C, which corresponds to 0.3% Zr and up to 10% Cu or Mg, is constructed.     

Microstructure and phase relations for Ti-Mo-Al alloys

The influence of aluminum additions to a Ti-7 at. pet Mo alloy on the phase equilibria was investigated. The microstructures of the alloys, Ti-7 pct Mo-7 pct Al and Ti-7 pct Mo-16 pct Al, were determined by light and electron microscopy. It was found that with increasing aluminum concentration the formation of the metastable w phase was suppressed. In the Ti-7 pct Mo-16 pct Al alloy the β phase decomposed upon quenching by precipitating coherent, ordered particles having a B2 type of crystal structure (β₂). At low temperatures the equilibrium phases for this alloy were β + α+ β ₂, whereas at high temperature (850° to 950°C) the Ti₃Al phase was in two-phase equilibrium with the β phase. The four-phase equilibrium which exists at a temperature of about 550°C involves the reaction β + Ti₃Al ⇌ α + β₂. G. LUETJERING, formerly Staff Member Materials Research Center, Allied Chemical Corp., Morristown, N. J.,     

Interdiffusion in Ni-Rich,Ni-Cr-Al alloys at 1100 and 1200 °C: Part I. Diffusion paths and microstructures

Interdiffusion in Ni-rich, Ni-Cr-Al diffusion couples was studied after annealing at 1100 and 1200 °C. Recession of γ′ (Ni₃Al structure), β (NiAl structure), or α (bcc) phases was also measured. Aluminum and chromium concentration profiles were measured in the γ (fcc) phase for most of the diffusion couples. The amount and location of Kirkendall porosity suggests that Al diffuses more rapidly than Cr which diffuses more rapidly than Ni in the γ phase of Ni-Cr-Al alloys. The location of maxima and minima in the concentration profiles of several of the diffusion couples indicates that both cross-term diffusion coefficients for Cr and Al are positive and that D_CrAl has a greater effect on the diffusion of Cr than does D_A1Cr on the diffusion of Al. The γ/γ + β phase boundary has also been determined for 1200 °C through the use of numerous γ/γ+ β diffusion couples.     

Diffusion of cobalt,chromium, and titanium in Ni3Al

Diffusion studies of cobalt, chromium, and titanium in Ni₃Al (γ′) at temperatures between 1298 and 1573 K have been performed using diffusion couples of (Ni-24.2 at. pct Al/Ni-24.4 at. pct Al-2.91 at. pct Co), (Ni-24.2 at. pct Al/Ni-23.1 at. pct Al-2.84 at. pct Cr), and (Ni-24.2 at. pct Al/Ni-20.9 at. pct Al-3.17 at. pct Ti). The diffusion profiles were measured by an electron probe microanalyzer, and the diffusion coefficients of cobalt, chromium, and tita-nium in γ′ containing 24.2 at. pct Al were determined from those diffusion profiles by Hall’s method. The temperature dependencies of their diffusion coefficients (m[su2]/s) are as follows: ~D_(Co) = (4.2 ± 1.2) × 1O^-3exp {-325 ± 4 (kJ/mol)/RT} ~D_(Cr) = (1.1 ± 0.3) × 10^-1 exp {-366 ± 3 (kJ/mol)/RT} and D_(Ti) = (5.6 ± 3.1) × 10¹ exp {-468 ± 6 (kJ/mol)/RT} The values of activation energy increase in this order: cobalt, chromium, and titanium. These activation energies are closely related to the substitution behavior of cobalt, chromium, and titanium atoms in the Ll₂ lattice sites of γ′; the cobalt atoms occupying the face-centered sites in the Ll₂ structure diffuse with the normal activation energy, whereas the titanium atoms oc-cupying the cubic corner sites diffuse with a larger activation energy that includes the energy due to local disordering caused by the atomic jumps. The chromium atoms which can occupy both sites diffuse with an activation energy similar to that of cobalt atoms.     

The Al-Cu-Fe phase diagram: 0 to 25 At. pct Fe and 50

Isothermal sections of the Al-Cu-Fe equilibrium phase diagram at temperatures from 680 °C to 800 °C were determined in the region with 50 to 75 at. pct Al and 0 to 25 at. pct Fe using scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) techniques. This re- gion includes the face-centered icosahedral phase (Ψ-Al₆Cu₂Fe) which has unprecedented struc- tural perfection and no apparent phason strain. The icosahedral phase has equilibrium phase fields with four distinct phases at 700 °C and 720 °C (β-Al(Fe, Cu), λ-Al₁₃Fe₄, ω-Al₇Cu₂Fe, and liquid) and three phases at 680 °C(β, ω, and λ) and 800 °C (β, λ, and liquid). The B2 ordered β phase has considerably greater solubility for Cu than previously reported, extending from AlFe to ∼Al₅₀Fe₅Cu₄₅. The equilibrium range of composition for the icosahedral phase at these temperatures was determined, and a liquidus projection is proposed.     

Selective oxidation and internal nitridation during high-temperature exposure of single-crystalline nickel-base superalloys

The process of internal nitridation of the three commercial single-crystalline nickel-base superalloys CMSX-2, CMSX-6, and SRR99 has been studied in air and oxygen-free nitrogen atmospheres at 800 °C to 1100 °C using thermogravimetric techniques supplemented by extensive microstructural examinations. Non-protective oxide formation, particularly cracking and spalling at edges or curved surfaces, enables nitrogen to penetrate into the alloy leading to the precipitation of stable Ti and Al nitrides. The high-temperature corrosion behavior of the superalloys studied is strongly affected by compositional differences between dendritic and interdendritic areas due to segregation resulting in an inhomogeneous internal precipitation zone. Furthermore, the stability of the strengthening γ′ phase (Ni₃(Al, Ti, Ta)) in front of the growing internal-nitridation zone was observed to depend clearly on the alloy composition. Therefore, the near-surface area of the alloys can be weakened by γ′ depletion and by embrittlement resulting from internal-nitride precipitation. The results obtained on the nickel-base superalloys are discussed, taking into account the results of a computer-based simulation of internal-corrosion processes. Furthermore, results on Ni-base model alloys of the system Ni-Cr-Al-Ti provided information on the role of the alloy composition. It was found that a higher Cr concentration seems to increase the nitrogen solubility and diffusion in Ni-base alloys.     

Characterization of microstructure in laser-surface-alloyed layers of aluminum on nickel

In order to obtain basic understanding of microstructure evolution in laser-surface-alloyed layers, aluminum was surface alloyed on a pure nickel substrate using a CO₂ laser. By varying the laser scanning speed, the composition of the surface layers can be systematically varied. The Ni content in the layer increases with increase in scanning speed. Detailed cross-sectional transmission electron microscopic study reveals complexities in solidification behavior with increased nickel content. It is shown that ordered B2 phase forms over a wide range of composition with subsequent precipitation of Ni₂Al, an ordered ω phase in the B2 matrix, during solid-state cooling. For nickel-rich alloys associated with higher laser scan speed, the fcc γ phase is invariably the first phase to grow from the liquid with solute trapping. The phase reorders in the solid state to yield γ′ Ni₃Al. The phase competes with β AlNi, which forms massively from the liquid. The β AlNi transforms martensitically to a 3R structure during cooling in solid state. The results can be rationalized in terms of a metastable phase diagram proposed earlier. However, the results are at variance with earlier studies of laser processing of nickel-rich alloys.