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.     

Investigation of microstructural changes in INCONEL 706 at high temperatures by In-Situ small-angle neutron scattering

The Ni-Fe based superalloy INCONEL 706 (IN706) has a complex microstructure and many A₃B type phases, e.g., Ni₃Al γ′, Ni₃Nb γ″, Ni₃Nb δ, or Ni₃Ti η precipitates can form. The various precipitates can also have different morphologies, i.e., plate, needle, cube, or disc shape, and some of them exist as co-precipitates—γ′/γ″. In the present study, in-situ measurements by small-angle neutron scattering (SANS) were performed to monitor the microstructural evolution at elevated temperatures. The SANS measurements were complemented by microstructural observations at room temperature by scanning electron microscopy and transmission electron microscopy (SEM and TEM). It is demonstrated that η plates and γ″ needles form directly at high temperatures. Cooling from high temperature produces fine dispersions of γ′/γ″ precipitates, which coarsen on reheating to lower stabilization temperatures (893 and 993 K). The final morphology of the γ′/γ″ co-precipitates, i.e., compact/noncompact type very much depends on the stabilization temperature and the cooling rates from prior higher-temperature stabilization steps.     

Morphology of y’ and y” precipitates and thermal stability of inconel 718 type alloys

The precipitation of the γ^’ (Ll₂) and γ^" (DO₂₂) phases has been studied in four alloys Fe-Ni-Cr-Ti-Al-Nb containing a higher Ti + Al/Nb ratio than that of the INCONEL 718 alloy. For these alloys, the precipitation microstructure varies rapidly with aging temperature and composition. Bct γ^"particles have always been found to precipitate on γ^’ phase. Moreover, by aging three alloys above a critical temperature, a “compact ntorphology” has been observed: cube-shaped γ^’ particles coated on their six faces with a shell of γ^" precipitate. This microstructure has proved to be very stable on prolonged aging. A thermal stability better than that encountered in nominal INCONEL 718 alloy can thus be achieved. The influence of composition and aging temperature on the conditions that bring about this “compact morphology” has been investigated. A minimal Ti + Al/Nb ratio between 0.9 and 1 has been determined, allowing the “compact morphology” to be obtained. This paper is based upon a thesis submitted by R. COZAR in partial fulfillment of the requirements of the degree of Doctor of Philosophy at the University of Nancy.     

Effect of strain rate on the high-temperature low-cycle fatigue properties of a nimonic PE-16 superalloy

Strain-rate effects on the low-cycle fatigue (LCF) behavior of a NIMONIC PE-16 superalloy have been evaluated in the temperature range of 523 to 923 K. Total-strain-controlled fatigue tests were performed at a strain amplitude of ±0.6 pct on samples possessing two different prior microstructures: microstructure A, in the solution-annealed condition (free of γ′ and carbides); and microstructure B, in a double-aged condition with γ′ of 18-nm diameter and M₂₃C₆ carbides. The cyclic stress response behavior of the alloy was found to depend on the prior microstructure, testing temperature, and strain rate. A softening regime was found to be associated with shearing of ordered γ′ that were either formed during testing or present in the prior microstructure. Various manifestations of dynamic strain aging (DSA) included negative strain rate-stress response, serrations on the stress-strain hysteresis loops, and increased work-hardening rate. The calculated activation energy matched well with that for self-diffusion of Al and Ti in the matrix. Fatigue life increased with an increase in strain rate from 3 × 10^-5 to 3 × 10^-3 s^-1, but decreased with further increases in strain rate. At 723 and 823 K and low strain rates, DSA influenced the deformation and fracture behavior of the alloy. Dynamic strain aging increased the strain localization in planar slip bands, and impingement of these bands caused internal grain-boundary cracks and reduced fatigue life. However, at 923 K and low strain rates, fatigue crack initiation and propagation were accelerated by high-temperature oxidation, and the reduced fatigue life was attributed to oxidation-fatigue interaction. Fatigue life was maximum at the intermediate strain rates, where strain localization was lower. Strain localization as a function of strain rate and temperature was quantified by optical and scanning electron microscopy and correlated with fatigue life.     

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.     

Behavior of a nickel-base high-temperature alloy under hot-working conditions

The behavior of a Ni-Cr-Co base alloy with significant additions of Mo, Ti and Al (Nimonic 105) under hot working conditions was studied using hot compression tests in the temperature range of 1223 to 1523 K and strain rates between 0.38 and 64.3 s^-1. The microstructure of the Nimonic 105 is complex and the matrix contains second phases in the form of Ni₃ (Ti, Al) dispersion (γ′), various Cr and Ti carbides and titanium cyanonitrides inclusions. However, the results show that above the dissolution temperature of the γ′ phase, the alloy behaves like a single phase nickel-base solid solution from the point view of steady state flow stress-temperature-strain rate relationships, and the activation energies for hot working and static recrystallization. Under deformation conditions where the γ′ phase is present, as in the case of creep, the activation energy is almost doubled. The hot working temperature range giving sound product is 1280 to 1450 K (170 K) at a strain rate of 0.4 s^-1 and decreases to 1400 to 1480 K (80 K) at a strain rate of 65 s^-1. At temperatures above the higher limit the alloy suffers intercrystalline cracks due to hot shortness and at temperatures below the lower limit the alloy suffers transcrystalline cracks due to excessive strain hardening.     

The columnar-to-equiaxed transition in Al 3 Pct Cu

A columnar-to-equiaxed transition is observed in Al 3 pct Cu solidified directionally from a chill face. The transition occurs when the temperature gradient in the melt ahead of the columnar dendrites decreases to 0.6 ‡C/cm at dendrite growth rates of about 5 x 10^-3 cm/s. Increasing the nuclei density by adding 171 ppm of TiB₂ to the melt produces a fine-grained structure without columnar growth. Adding 100 ppm TiB₂ has no effect on the cast structure or columnar-to-equiaxed transition. The results are considered in relation to the model for the columnar-to-equiaxed transition proposed by Hunt.^[2]     

Phase equilibria in the Ni-Al-Ti system at 1173 k

The phase equilibria at 1173 K have been determined in the Ni-AI-Ti system for Al contents less than 50 at. pct. The extent of theH (Ni₂AlTi) phase field has been established as well as the extent of solubility in the binary compounds γ (Ni₃Al), ν(Ni₃Ti), β₂(NiTi), NiTi₂, and ζ(AlTi₃). Substantial differences were found between the phase equilibria determined in this study and previous studies, in part due to the large solubility of Al in NiTi₂.     

Hydrogen transport in nickel-base alloys

The electrochemical permeation technique has been used to characterize hydrogen transport and trapping in pure nickel and in alloys 600, X-750, and 718 at a temperature of 80 °C. The “effective diffusivity” of hydrogen atoms in alloy 600 is reduced by a factor of about 5 compared to pure nickel. This is attributed to both compositional changes and the presence of [(Ti, Nb)C] carbides. Aging of alloy 600, with subsequent M₂₃C₆ carbide precipitation, does not significantly influence the measured “effective diffusivity,” which is explained by the dominant effect of preexisting [(Ti, Nb)C] carbides. The “effective diffusivity” of hydrogen atoms in solution-annealed alloy X-750 is reduced by a factor of about 9 compared to that of pure nickel. This is also attributed to compositional changes and [(Ti,Nb)C] carbides. Aging of alloy X-750, which causes precipitation of γ’[Ni₃(Al, Ti)], reduces the “effective diffusivity” by an additional factor of 5 or more. Double aging at 885 °C/24 hours, 704 °C/20 hours following hot working yields the greatest reduction in “effective diffusivity.” Analysis of permeation transients using a diffusiontrapping model indicates a binding energy associated with trapping due to the γ’ phase of between-31 and -37 kJ/mol. The “effective diffusivity” of hydrogen in alloy 718 is about 40 pct greater than for alloy X-750 for the same double and direct aging treatments. The average “effective diffusivities” of the double-aged and direct-aged alloy 718 are comparable, but the permeation transients for the double-aged treatment are significantly steeper. The double-aged treatment with predominantly S phase (orthorhombic Ni₃Nb) yields a binding energy of about-30 kJ/mol. Analysis of the direct aged-treated 718, which contains predominantly γ′ phase (body-centered tetragonal Ni₃Nb) gave a binding energy between -23 and -27 kJ/mol. Segregation of hydrogen atoms to the γ′/matrix interface, combined with a large volume fraction ofγ at grain boundaries, provides the most likely explanation for the enhanced cracking associated with the double-aging treatment in alloy X-750.     

Phase chemistry and precipitation reactions in maraging steels: Part I. Introduction and study of Co-containing C-300 steel

This article introduces a series of studies of phase transformations in maraging steels. Atom-probe field-ion microscopy (APFIM) was the main research technique employed. Hardness measurements, transmission electron microscopy (TEM), and thermochemical calculations were also used. The composition and morphology of precipitates in the commercial-grade C-300 steel were compared for different aging times at 510 °C to investigate the aging sequence. Both Ni₃Ti and Fe₇Mo₆ were found to contribute to age hardening. The decomposition starts with the formation of small Mo-enriched Ni₃Ti particles at very short aging times. The Fe₇Mo₆ phase forms at a later stage of aging. The matrix concentrations of both Ti and Mo were measured and were found to be low after standard aging conditions. The observation of the Fe₇Mo₆ μ phase is supported by thermochemical calculations. Austenite reversion has been found at the aging temperature, and its composition approaches the predicted equilibrium composition after 8 hours of aging. Formerly Graduate Student with the Department of Materials, Oxford University.     

Precipitation of heusler phase (Ni<Subscript>2</Subscript>TiAl) from B2-TiNi in Ni-Ti-Al and Ni-Ti-Al-X (X=Hf,Zr) alloys

The precipitation of Heusler phase (L2₁: Ni₂TiAl) from a supersaturated B2 (TiNi-based) matrix at 600°C and 800°C is studied using transmission electron microscopy (TEM), analytical electron microscopy (AEM), and three-dimensional atom-probe (3DAP) microscopy in Ni-Ti-Al and Ni-Ti-Al-X (X=Hf and Zr) alloys. The B2/L2₁ two-phase system, with ordered structures based on the bcc lattice, is chosen for its microstructural analogy to the classical γ/γ′ system with an fcc lattice. Knowledge of the temperature-dependent partitioning of alloying elements and their atomic volumes in the B2-TiNi and L2₁ phases is desired to support design of high-performance shape-memory alloys (SMAs) with controlled misfit strain and transformation temperatures. After aging at 600°C for up to 2000 hours, the L2₁ precipitates remain fully coherent at a particle diameter of ∼20 nm. The observed effects of a misfit strain of −1.9 pct on the microstructure of the B2/L2₁ system are similar to those theoretically predicted and experimentally observed for the γ/γ′ system. The similarities are demonstrated in terms of the precipitate shape, spatial distribution, and minimum distance of separation between L2₁ precipitates. However, all these effects disappear after aging the alloys at 800°C for 1000 hours, when the L2₁ precipitates become semicoherent at particle diameters above ∼400 nm. A simple analysis of the size evolution of L2₁ precipitates after an isochronal aging (1000 hours) experiment suggests that they follow coarsening kinetics at 600°C and growth kinetics at 800°C, consistent with the Langer-Schwartz theory of precipitation kinetics, which predicts that a high supersaturation suppresses the growth regime. Microanalysis using AEM and 3DAP microscopy define the TiNi-Ni₂TiAl phase boundaries at 800°C and 600°C. At 800°C, Hf and Zr partition to the B2-TiNi, while at 600°C, they partition slightly to the L2₁ phase, reducing the lattice misfit to −1.7 and −0.011 pct, respectively, and partition strongly to the metastable phase Ti₂Ni₃. To describe the composition dependence of the lattice parameter of multicomponent B2 and L2₁ phases, the atomic volumes of Al, Hf, Ni, Ti, and Zr in the B2-TiNi and L2₁ phases are determined. A simple model is proposed to predict the lattice parameters of these phases in multicomponent systems.     

Development of TiB<Subscript>2</Subscript> reinforced in-situ Ti aluminide matrix composite through reaction synthesis

TiB₂ reinforced in-situ titanium aluminide matrix composite was made through reaction synthesis process using high purity elemental powders of Ti, Al, Cr, Nb and B. XRD of the synthesized block showed presence of mainly Al₃Ti and TiB₂ phases. To obtain γ Ti aluminide based matrix, the material was homogenized in two phase region (α₂+γ). Presence of γ phase matrix alongwith α₂ was confirmed through XRD, SEM and TEM. Uniform distribution of TiB₂ phase was confirmed through elemental mapping and by analyzing specimens of different locations. Differential scanning calorimetry of powder mixture showed presence of endothermic peak for Al melting and exothermic peak of Ti aluminide and TiB₂ formation.     

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.     

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.     

The enhancement of strengthening dislocated martensite

The basis of this work was the investigation of improving the tensile properties of dislocated martensites by dispersion of precipitates in the austeniteprior to the martensite transformation. Two types of precipitation-hardenable austenitic alloys were used. One is based on Fe-22 Ni-4 Mo-0.28 C where the precipitates are Mo₂C and are obtained by ausforming and aging, and the other is Fe-28 Ni-2 Ti where the precipitates are the coherent fccγ’ (Ni₃Ti) ordered phase obtained by ausaging. After the austenitic dispersion treatment both alloys were transformed to martensite by quenching to liquid nitrogen and the properties measured and compared to martensites obtained by conventional heat treatment (i.e. no precipitates in austenite). The results show that prior dispersions increase the strength of martensite and this is interpreted as being due to an increase in dislocation density resulting from dislocation multiplication at the particles during the γ →M _s transformation. In addition, the stabilities of the austenitic alloys are such that upon certain aging treatments, the alloys transform partially to martensite (due to precipitation) and “composite” materials are obtained whose strength depends on the volume fraction and yield strengths of the phases present. Formerly Graduate Student, Department of Materials Science and Engineering, University of California, Berkeley, Calif.     

Microstructure and hydrogen performance of alloy 903

Transmission electron microscopy has been used to determine that the strengthening precipitate in Incoloy 903 is γ′ (Ni₃ (Al, Ti)), with no evidence of γ″ (Ni_xNb), although the latter has been reported. In addition, the alloy does not undergo a martensitic transformation when quenched to 4 K in the solution treated or aged conditions. Aged tensile specimens charged with 1200 at. ppm of hydrogen exhibited ductility losses when compared to uncharged specimens. The hydrogen-charged specimens failed in a ductile manner, the fracture being characterized by a finer dimple size than observed in uncharged specimens. The ductility loss is shown to be a function of the dimple size reduction (expressed as the ratio of dimple size with hydrogen to that without hydrogen) and can be explained in terms of accelerated dimple nucleation due to hydrogen accumulation at precipitate particles.     

Auger electron analysis of the initial oxidation of titanium aluminides based on Ti-48Al

The surface of a Ti-48 at. Pct Al alloy was examined by Auger electron microscopy to study oxidation at room temperature. On exposure to air at room temperature, both Al and Ti oxides were observed together with an abundance of C. The amount of C was always larger in the two-phase α₂ + γ region compared to the single-phase γ region. The Ti oxides formed on the surface of they grains were primarily Ti₂O₃ rather than TiO₂. On depth profiling with Ar⁺ ion sputtering, lower oxide states of Ti were found. This was attributed to either the Ar⁺ ion sputtering or the fact that the inner layers of oxide represented oxides of Ti in their lower valence states. The A1₂O₃ was stable and did not exhibit any transient oxidation states. The dominant oxidation product on the surface of sputtered single-phase γ grains after an 84-hour exposure in the ultrahigh vacuum Auger chamber at room temperature is A1₂O₃. A depletion of C and O occurred beneath the oxide surface in some γ grains. The chemical shift between the Al L_2,3MM and A1₂O₃ L_2,3(A1)M_(O)M_(O) peaks in the Auger spectrum of A1₂O₃ formed on the γ phase in TiAl was found to be 11 eV. Y.T. Peng, Graduate Student, Formerly with the Materials Science and Engineering Program, University of Texas at Arlington, Arlington, TX 76019,     

Microstructures and mechanical properties of Ni3Al alloyed with iron additions

The alloying behavior of iron in B-doped Ni₃Al was studied using optical and transmission electron microscopy for microstructural analysis and tensile testing for mechanical property evaluation. The aluminide dissolves less than 15 at. pct iron. At iron levels of 15 pct, depending on the aluminum level, formation of both transformed B2 phase (β^′) and disordered fee phase (γ) is observed. The phase relationships in the aluminide containing 10 pct iron were studied in detail by quenching from temperatures below 1370 °C. Tensile properties of nickel-iron aluminides were determined as functions of iron content and test temperature. The tensile results are discussed in terms of solid-solution hardening, atomic size misfit, and precipitation of γ, β^′, and carbides.     

Deformation behavior of a Ni3Al(B,Zr) alloy during cold rolling: Part I. changes in order and structure

A hypostoichiometric Ni₃Al(B,Zr) alloy was homogenized and cold rolled by amounts ranging from 25 to 73 pct. The alloy consisted of two phases—a partially ordered γ′ phase (L1₂) and a Ni-rich fcc solid solution (γ). On deforming the alloy by rolling at room temperature, the order parameter showed a gradual change. In fact, between 35 and 45 pct deformation, the order characteristic of the L1₂ structure changed into that of a DO₂₂ structure. The possibility of transition from L1₂ to DO₂₂ structure is also corroborated from strain parameter, microhardness, and detailed x-ray diffraction (XRD) measurements. This structural transformation is accompanied by a change in the deformation mode (from slip to twinning), as is evident from the relevant microstructures.     

Compositional Variations between Different Generations of <Emphasis Type="Italic">γ</Emphasis>′ Precipitates Forming during Continuous Cooling of a Commercial Nickel-Base Superalloy

The compositional and microstructural evolution of different generations of precipitates of the ordered γ′ phase during the continuous cooling, followed by isothermal aging, of a commercial nickel-base superalloy, Rene 88DT, has been characterized by three-dimensional atom probe (3DAP) tomography coupled with energy-filtered transmission electron microscopy (EFTEM) studies. After solutionizing in the single γ-phase field, during continuous cooling at a relatively slow rate (~24 °C/min), the first-generation primary γ′ precipitates, forming at relatively higher temperatures, exhibit near-equilibrium compositions, while the smaller-scale secondary γ′ precipitates, forming at lower temperatures, exhibit nonequilibrium compositions often containing an excess of Co and Cr while being depleted in Al and Ti content. The compositions of the γ matrix near these precipitates also exhibit similar trends, with the composition being closer to equilibrium near the primary precipitates as compared to the secondary precipitates. Subsequent isothermal aging at 760 °C leads to coarsening of the primary γ′ precipitates without affecting their composition significantly. In contrast, the composition of the secondary γ′ precipitates is driven toward equilibrium during the isothermal aging process.