The effect of orientation and sense of applied uniaxial stress on the morphology of coherent gamma prime precipitates in stress annealed nickel-base superalloy crystals

The coarsening of coherent γ′[Ni₃(Al, Ti)] precipitates in single crystals of a representative nickel-base superalloy, Udimet-700, is shown to be affected by a uniaxial stress applied during annealing. Depending on the sense of the applied stress and its crystallographic orientation, stress annealing results in oriented cuboidal, plate, or parallelepiped shaped γ′ precipitates. A general thermodynamic analysis of the effect of stress annealing on precipitate morphology is presented that takes into account free energy changes due to changes in bulk precipitation strain, effective modulus, coherency strain energy, and the total interphase boundary area. The analysis correctly predicts the observed γ′ precipitate morphologies as a function of stress axis orientation, stress sense, the lattice misfit of the precipitate phase, and the elastic constants of the matrix and precipitate phases. The analysis also shows that stress induced morphological changes can be completely precluded, as may be desired to optimize mechanical behavior, only if the elastic constants of the matrix and precipitate phases are equal. Changes in morphology due to changes in bulk precipitation strain, which in the case of Udimet-700 is shown to be the dominant effect, can be eliminated by alloying for zero lattice misfit or, in single crystals, by stressing parallel to < 111> . Applications to long-term creep behavior and to the fabrication of composite structures are discussed. Formerly with Advanced Materials Research and Development Laboratory, Pratt & Whitney Aircraft     

铁/镍基奥氏体多晶合金晶界弯曲研究进展

对于在高温环境服役的金属材料,晶界作为组织结构上的薄弱环节常常引发晶界裂纹而造成合金失效,严重影响了材料的高温力学性能表现。因而,如何改善晶界状态、提高晶界强度,是提高合金高温性能的关键。在铁/镍基奥氏体多晶合金中,采用晶界弯曲的方法强化晶界、改善合金性能一直受到国内外研究人员的广泛关注。从弯曲晶界的获得方法、形成机制及其对材料性能的影响3个方面概述了目前国内外的研究现状。较为全面地总结了特殊热处理与材料合金化等获得弯曲晶界的方法;讨论了不同合金中晶界第二相诱发晶界弯曲的驱动力和内在机理;介绍了弯曲晶界对材料力学性能、耐蚀性能及焊接性能的影响。最后,结合当前的研究现状,围绕弯曲晶界的形成条件和机制,以及弯曲晶界对性能的影响,提出了弯曲晶界未来的研究发展方向。      

The effect of uniaxial stress on the periodic morphology of coherent gamma prime precipitates in nickel-base superalloy crystals

The periodic morphology of cube shaped, coherent γ ′ [Ni₃(Al, Ti)] precipitates in a representative nickel-base superalloy single crystal is shown to be influenced by the application of a 〈100〉 oriented uniaxial stress during annealing at elevated temperature. Furthermore, the stress annealed γ′ morphologies depend on the stress sense. Tensile and compressive stress annealing result in a directional coarsening of precipitates, and then agglomeration to form γ ′ precipitate plates with broad faces aligned perpendicular to the stress axis and precipitate parallelepipeds with long axes parallel to the stress axis, respectively. In explaining the morphological changes that occur during stress annealing, we consider two driving forces: i) a driving force due to changes in the stress-free shape of the specimen, and ii) a driving force due to changes in the effective modulus of the specimen. The first, which depends on a difference in the elastic constants and the lattice parameters of the two phases, is apparently the dominant driving force for the observed morphological changes in a stress annealed superalloy. The second, which depends only on a difference in elastic constants, may be important in alloys with elastically soft, incoherent inclusions such as pores. Formerly Section Supervisor, Advanced Materials Research and Development Laboratory, Pratt & Whitney Aircraft.     

Threshold Stress Creep Behavior of Alloy 617 at Intermediate Temperatures

Creep of Alloy 617, a solid solution Ni-Cr-Mo alloy, was studied in the temperature range of 1023 K to 1273 K (750 °C to 1000 °C). Typical power-law creep behavior with a stress exponent of approximately 5 is observed at temperatures from 1073 K to 1273 K (800 °C to 1000 °C). Creep at 1023 K (750 °C), however, exhibits threshold stress behavior coinciding with the temperature at which a low volume fraction of ordered coherent γ′ precipitates forms. The threshold stress is determined experimentally to be around 70 MPa at 1023 K (750 °C) and is verified to be near zero at 1173 K (900 °C)—temperatures directly correlating to the formation and dissolution of γ′ precipitates, respectively. The γ′ precipitates provide an obstacle to continued dislocation motion and result in the presence of a threshold stress. TEM analysis of specimens crept at 1023 K (750 °C) to various strains, and modeling of stresses necessary for γ′ precipitate dislocation bypass, suggests that the climb of dislocations around the γ′ precipitates is the controlling factor for continued deformation at the end of primary creep and into the tertiary creep regime. As creep deformation proceeds at an applied stress of 121 MPa and the precipitates coarsen, the stress required for Orowan bowing is reached and this mechanism becomes active. At the minimum creep rate at an applied stress of 145 MPa, the finer precipitate size results in higher Orowan bowing stresses and the creep deformation is dominated by the climb of dislocations around the γ′ precipitates.     

Stress Rupture Fracture Model and Microstructure Evolution for Waspaloy

Stress rupture behavior and microstructure evolution of nickel-based superalloy Waspaloy specimens from tenon teeth of an as-received 60,000-hour service-exposed gas turbine disk were studied between 923 K and 1088 K (650 °C and 815 °C) under initial applied stresses varying from 150 to 840 MPa. Good microstructure stability and performance were verified for this turbine disk prior to stress rupture testing. Microstructure instability, such as the coarsening and dissolution of γ′ precipitates at the varying test conditions, was observed to be increased with temperature and reduced stress. Little microstructure variation was observed at 923 K (650 °C). Only secondary γ′ instability occurred at 973 K (700 °C). Four fracture mechanisms were obtained. Transgranular creep fracture was exhibited up to 923 K (650 °C) and at high stress. A mixed mode of transgranular and intergranular creep fracture occurred with reduced stress as a transition to intergranular creep fracture (ICF) at low stress. ICF was dominated by grain boundary sliding at low temperature and by the nucleation and growth of grain boundary cavities due to microstructure instability at high temperature. The fracture mechanism map and microstructure-related fracture model were constructed. Residual lifetime was also evaluated by the Larson–Miller parameter method.     

Microstructures induced by a stress gradient in a nickel-based superalloy

The evolution of the microstructure of single crystals of a nickel-based superalloy during high temperature (1323 K, 1050°C) creep in bending has been studied. Bending provides both tensile and compressive stress gradients; consequently the effects of varying stress conditions on the evolution of the morphology of the γ′ precipitates can be determined from a single specimen. The morphological changes were analysed by scanning electron microscopy using image analysis techniques and by transmission electron microscopy, then described by dimensionless parameters. We discuss the dependence of the morphological changes in the superalloy on the stresses acting in the sample (magnitude and sign). We also discuss the driving mechanisms for the observed morphological changes.     

Constrained cavity growth models of longitudinal creep deformation of oxide dispersion strengthened alloys

Two models of constrained cavity growth are developed to describe the long-term longitudinal creep behavior of nickel based oxide dispersion strengthened (ODS) alloys. For both models the rupture time is taken as the time for a transverse grain boundary to cavitate fully. A diffusive cavity growth law is assumed to govern cavitation. The applicability of the respective models is determined by the particular grain morphology achieved by thermal-mechanical processing. The first model assumes that longitudinal grain boundaries are unable to slide; hence displacements due to cavitation must be matched by displacements due to dislocation creep in adjoining grains. This model predicts a low stress exponent at the transition from single crystal to cavitation creep behavior, and higher stress exponents at stresses below this transition. Good agreement is found between the model predictions and creep data for MA 754 at 1000 and 1093 °C. A second model considers a grain morphology wherein longitudinal grain boundaries are able to slide by means of deformation of pockets of fine grains. Cavitation of transverse grain boundaries is thus controlled by grain boundary sliding. This model predicts a stress exponent of 1 at low stresses, and serves as an upper bound for the creep rate when a duplex grain morphology is present. Model predictions are in good agreement with creep data for a heat of MA 754 with a duplex grain morphology. Formerly Graduate Research Assistant in the Department of Materials Science and Engineering at Stanford University     

Morphological changes of carbides during creep and their effects on the creep properties of inconel 617 at 1000 °C

Creep tests have been correlated with microstructural changes which occurred during creep of Inconel 617 at 1000 °C, 24.5 MPa. The following results were obtained: 1) Fine intragranular carbides which are precipitated during creep are effective in lowering the creep rate during the early stages of the creep regime (within 300 h). 2) Grain boundary carbides migrate from grain boundaries that are under compressive stress to grain boundaries that are under tensile stress. This is explained in terms of 1 the dissolution of relatively unstable carbides on the compressive boundaries, 2 the diffusion of the solute atoms to the tensile boundaries and 3 the reprecipitation of the carbides at the tensile boundaries. The rate of grain boundary carbide migration depends on grain size. 3) M₂₃C₆ type carbides, having high chromium content, and M₆C type carbides, having high molybdenum content, co-exist on the grain boundaries. M₂₃C₆ type carbides, however, are quantitatively predominant. Furthermore, M₆C occurs less frequently on the tensile boundaries than on the stress free grain boundaries. This is attributed to the difference of the diffusion coefficients of chromium and molybdenum. 4) The grain boundaries on which the carbides have dissolved start to migrate in the steady state creep region. The creep rate gradually increases with the occurrence of grain boundary migration. 5) The steady state creep rate depends not so much on the morphological changes of carbides as on the grain size of the matrix.     

Creep and rupture of an ods alloy with high stress rupture ductility

The creep and stress rupture properties of an oxide (Y₂O₃) dispersion strengthened nickel-base alloy, which also is strengthened by γ′ precipitates, was studied at 760 °C and 1093 °C. At both temperatures the alloy YDNiCrAl exhibits unusually high stress rupture ductility as measured by both elongation and reduction in area. Failure was transgranular, and different modes of failure were observed including crystallographic fracture at intermediate temperatures and tearing or necking almost to a chisel point at higher temperatures. While the rupture ductility was high, the creep strength of the alloy was low relative to conventional γ′ strengthened superalloys in the intermediate temperature range and to ODS alloys in the higher temperature range. These findings are discussed with respect to the alloy composition; the strengthening oxide phases, which are inhomogeneously dispersed; the grain morphology, which is coarse and elongated and exhibits many included grains; and the second phase inclusion particles occurring at grain boundaries and in the matrix. The creep properties, in particular the high stress dependencies and high creep activation energies measured, are discussed with respect to the resisting stress model of creep in particle strengthened alloys. RICHARD M. ARONS, formerly a Graduate Student at Columbia University     

Effect of prior creep at 1365 K on the room temperature tensile properties of several oxide dispersion strengthened alloys

A study was undertaken to determine if oxide dispersion strengthened (ODS) Ni-base alloys in wrought bar form are subject to a loss of room temperature tensile properties after elevated temperature creep similar to that found in a thin gage ODS alloy sheet. The bar products evaluated included ODS-Ni, ODS-NiCr, and advanced ODS-NiCrAl types. Tensile type test specimens were creep exposed in air at various stress levels at 1365 K and then tensile tested at room temperature. Low residual tensile properties, change in fracture mode, the appearance of dispersoid free bands, grain boundary cavitation, and/or internal oxidation in the microstructure were interpreted as creep degradation effects. This work has shown that many ODS alloys are subject to creep damage. Degradation of tensile properties occurs after very small amounts (≲0.2 pct) of creep strain; ductility being the most sensitive property. The amount of degradation is dependent on the creep strain and is essentially independent of the alloy system. All the ODS alloys which were creep damaged possessed a large grain size (>100 μm). Creep damage appears to be due to diffusional creep which produces dispersoid free bands around boundaries acting as vacancy sources. Low angle and, possibly, twin boundaries were found to act as vacancy sources. The residual tensile properties of two alloys were not affected by prior creep parallel to the extrusion axis. One of these alloys, DS-NiCr(S), was single crystalline. The other alloy, TD-Ni, possessed a small, elongated grain structure which minimized the thickness of the dispersoid free bands produced by diffusional creep.     

Evolution of Grain Boundary Precipitates in an Al-Cu-Li Alloy During Aging

The grain boundary microstructure of Al-Cu-Li alloy AA2050 was investigated for different isothermal aging times to rationalize intergranular corrosion (IGC) characteristics. In the underaged condition, the dominant grain boundary precipitates are fine T₁ (Al₂CuLi). Extended aging revealed that grain boundaries were decorated by large T₁ precipitates and S′ phase (Al₂CuMg), with S′ growth not dimensionally constrained. Such a transition in the precipitate type at grain boundaries is a unique feature of the Al-Cu-Li system.     

A study of grain boundary nucleated widmanstätten precipitates in a two-phase stainless steel

The factors which control the nucleation and growth of Widmanstätten precipitates at grain boundaries in a two-phase stainlesss steel, have been studied by transmission electron microscopy. Widmanstätten precipitates usually involves a separate nucleation and growth event at prior austenite films or allotriomorphs, which are the first phase to form at grain boundaries. The Widmanstätten precipitates have a preferred orientation relationship with both the prior grain boundary γ-phase and with the α matrix. The particular γ variant which forms has a near Kurdjumov-Sachs relationship with the α-grain and the invariant line assciated with the variant is nearly normal to the grain boundary plane. The orientation relationship changes during growth, towards an exact K-S relationship, with the growth direction (which is parallel to the invariant line) also rotating to be nearly parallel to the common close-packed direction associated with the transformation.     

Nucleation of grain boundary cavities under the combined influence of helium and applied stress

Modelling cavity nucleation at grain boundaries in structural alloys under the combined influence of helium and stress is the primary objective of this paper. The role of stress in cavity nucleation is analyzed using an extension of classical theory by taking into account grain boundary sliding to describe stress concentration buildup and relaxation at particles and triple-point junctions. Helium clustering in the matrix is modeled using rate theory. The helium flux to grain boundaries is determined by the application of sink strength theory which takes into account the various competing clustering mechanisms in the matrix. Helium clustering on grain boundaries is also theoretically investigated using rate theory. The work agrees with experimental observations showing that irradiation results in grain boundary bubble densities which are orders of magnitude larger than cavity populations observed in conventional creep experiments. It is shown that even if the total injected helium is as little as one part per million, it can result in grain boundary bubble densities on the order of 10¹³ m⁻². Such cavity population exceeds typical grain boundary cavity densities associated with creep experiments. Grain boundary bubble densities are shown to reach steady state for injected helium amounts on the order of 10 parts per million.     

Calculation of the internal stresses and strains in the microstructure of a single crystal nickel-base superalloy during creep

The evolution of internal stresses and strains in the microstructure of a single crystal nickel-base alloy during annealing and during creep in [001] direction has been calculated using a visco-plastic model. Two limiting conditions are considered: an “overloading” case where the internal stresses reach the critical resolved shear stress of the whole γ′ volume and an “underloading” case where the critical resolved shear stress of the γ′ precipitate is reached only at distinct areas. During creep deformation a triaxial stress state evolves in the microstructure and large pressure gradients are built up. The influence of an initial coherency misfit is shown to be negligible after short times of creep. The calculations allow the prediction of flow patterns in the microstructure, creep-induced lattice parameter changes, type and arrangement of interfacial dislocations and of the dependence of the stationary strain rate on the cube or plate morphology of the γ′ phase.     

Microstructural study: an aid to determination of failure mechanism in nickel base superalloy blades

Cast nickel base superalloys are extensively used for high temperature gas turbine blade applications. The elevated temperature properties in these alloys are optimized through engineered microstructure, which is a combination of (a) γ-solid solution of Ni with elements such as W, Mo, Cr, Ta, Re etc, (b) γ′ precipitates, and (c) dispersed carbides. Over the years, the demand for high engine efficiency has resulted in the development of new generation superalloys with improved elevated temperature properties, especially creep resistance. These superalloys are highly alloyed with solid-solution strengthening elements and hence, impose greater technological challenges in fabrication. Due to high alloy contents, these alloys are prone to formation of detrimental phases such as the topologically close packed (TCP) phases. These phases may appear in the microstructure during the blade fabrication stages or precipitate out during exposure to high temperature and stress. In addition, the γ′ precipitates can change in morphology, shape and size during applications resulting in deterioration in high temperature mechanical properties, in general. These unfavorable microstructural changes often lead to premature failure in gas turbine engines. While analyzing these failures, the microstructural study provides important information in identifying whether the blades had faulty microstructure to start with or the abnormalities observed have resulted during exposure to service conditions. This in turn can be related to engine operating conditions. In the present paper, this has been demonstrated through analysis of two service failure cases wherein the high pressure turbine blades had failed in flight leading to aircraft accidents.     

Grain boundary γ″ precipitation and niobium segregation in inconel 718

The grain boundary γ″ precipitates in a commercial Inconel 718 have been critically examined by TEM. The results show that the grain boundaries were almost fully covered with γ″ particles which can account for the previous XPS finding of grain boundary enrichment in niobium for this alloy. These grain boundary γ″ precipitates appear to be disc-shaped, lie on the boundary plane, and have no habit-plane relationship with either of the neighboring grains. This finding suggests that the γ″ precipitates formed as a result of niobium segregation at the grain boundaries, rather than having the grain boundaries acting simply as the nucleation sites for preferential precipitation.     

Novel hafnium containing steels for power generation

Abstract

There is clear evidence that creep damage in power plant steels is associated with grain boundary precipitates. These particles provide favourable nucleation sites for grain boundary cavities and microcracks. The formation of M₂₃C₆ carbides as grain boundary precipitates can also lead to grain boundary chromium depleted zones which are susceptible to corrosive attack. Such precipitates are the causing loss of creep life in the later stages of creep because of their very high coarsening rate. Through Monte Carlo based grain boundary precipitation kinetics models, combined with continuum creep damage modelling it is predicted that improvements in creep behaviour of power plant steels can be achieved by increasing the proportion of MX type particles. Studies of a Hf containing steel have produced improvements in both creep and corrosion properties of 9%Cr steels. Hf has been ion implanted into thin foils of a 9 wt-%Cr ferritic steel to study its effect on precipitation. Two new types of precipitates are formed, Hf carbide, (an MX type precipitate) and a Cr–V rich nitride, with the formula M₂N. The Hf carbide particles were identified using convergent beam diffraction techniques, and micro-analysis. The nanosized particles are present in much higher volume fractions when compared to VN volume fractions in conventional power plant ferritic steels. Furthermore it is confirmed that the Hf causes the removal of M₂₃C₆ grain boundary precipitates. This has led to an increased concentration of Cr within the matrix, reduced chromium depleted zones at grain boundaries, and increased resistance to intergranular corrosion cracking.     

Heterogeneous Creep Deformations and Correlation to Microstructures in Fe-30Cr-3Al Alloys Strengthened by an Fe<Subscript>2</Subscript>Nb Laves Phase

A new Fe-Cr-Al (FCA) alloy system has been developed with good oxidation resistance and creep strength at high temperature. The alloy system is a candidate for use in future fossil-fueled power plants. The creep strength of these alloys at 973 K (700 °C) was found to be comparable with traditional 9 pct Cr ferritic–martensitic steels. A few FCA alloys with general composition of Fe-30Cr-3Al-.2Si-xNb (x = 0, 1, or 2) with a ferrite matrix and Fe₂Nb-type Laves precipitates were prepared. The detailed microstructural characterization of samples, before and after creep rupture testing, indicated precipitation of the Laves phase within the matrix, Laves phase at the grain boundaries, and a 0.5 to 1.5 μm wide precipitate-free zone (PFZ) parallel to all the grain boundaries. In these alloys, the areal fraction of grain boundary Laves phase and the width of the PFZ controlled the cavitation nucleation and eventual grain boundary ductile failure. A phenomenological model was used to compare the creep strain rates controlled by the effects of the particles on the dislocations within the grain and at grain boundaries. (The research sponsored by US-DOE, Office of Fossil Energy, the Crosscutting Research Program).     

Elimination of precipitate free zones in an Fe−Nb creep-resistant alloy

Precipitation of the Fe₂Nb intermetallic compound has previously been found to cause substantial hardening during aging of Fe rich Fe-Nb alloys. However, the formation of a wide precipitate free zone adjacent to the grain boundaries caused a degradation of creep resistance. In an effort to decrease the precipitate free zone width, thereby improving the creep resistance, an extensive study was made of the precipitation behavior of an Fe-1.7 at. pct Nb(Cb) alloy quenched from the δ-phase field. The quenched alloy was found to decompose via a two step reaction during aging at temperatures below 550°C. The first step in the decomposition reaction is thought to occur by clustering of Nb atoms in the ferrite matrix, similar to the clustering of Mo atoms which is known to occur during aging of Fe-Mo alloys. The second step in the reaction is not well understood. The precipitate free zones were formed by solute depletion in the vicinity of the grain boundary and the subsequent difficulty of nucleation of the Fe₂Nb precipitates in the regions of lowered solute concentration. Using two step aging treatments, an initial low temperature step to develop the Nb atom clusters followed by a higher temperature step to cause Fe₂Nb precipitation, the precipitate free zones were eliminated from the aged alloys. The origin of this effect is thought to be the heterogeneous nucleation of Fe₂Nb precipitates on the clusters developed during the initial aging step.