Solidification of Nb-bearing superalloys: Part I. Reaction sequences

The solidification reaction sequences of experimental superalloys containing systematic variations in Fe, Nb, Si, and C were studied using differential thermal analysis (DTA) and microstructural characterization techniques. The reaction sequences responsible for microstructural development were found to be similar to those expected in the Ni-Nb-C ternary system and commercial superalloys of comparable composition. The solute-rich interdendritic liquid generally exhibited two eutectic-type reactions at the terminal stages of solidification: L → (γ+NbC) and L → (γ+Laves). The Ni-base alloys with a high C/Nb ratio represented the only exception to this general solidification sequence. This group of alloys terminated solidification with the L → (γ + NbC) reaction and did not exhibit the γ/Laves constituent. At similar levels of solute elements (Nb, Si, and C), the Fe-base alloys always formed more of the γ/Laves eutectic-type constituent than the corresponding Ni-base alloys. Silicon additions also increased the amount of the γ/Laves constituent that formed in the assolidified microstructure, while C additions promoted formation of γ/NbC. The influence of Nb was dependent on the C content of the alloy. When the C content was low, Nb additions generally promoted formation of γ/Laves, while Nb additions to alloys with high C led to formation of the γ/NbC constituent. The results of this work are combined with quantitative analyses for developing γ-Nb-C pseudoternary solidification diagrams in a companion article.     

On the Effect of Nb on the Microstructure and Properties of Next Generation Polycrystalline Powder Metallurgy Ni-Based Superalloys

The effect of Nb on the properties and microstructure of two novel powder metallurgy (P/M) Ni-based superalloys was evaluated, and the results critically compared with the Rolls-Royce alloy RR1000. The Nb-containing alloy was found to exhibit improved tensile and creep properties as well as superior oxidation resistance compared with both RR1000 and the Nb-free variant tested. The beneficial effect of Nb on the tensile and creep properties was due to the microstructures obtained following the post-solution heat treatments, which led to a higher γ′ volume fraction and a finer tertiary γ′ distribution. In addition, an increase in the anti-phase-boundary energy of the γ′ phase is also expected with the addition of Nb, further contributing to the strength of the material. However, these modifications in the γ′ distribution detrimentally affect the dwell fatigue crack-growth behavior of the material, although this behavior can be improved through modified heat treatments. The oxidation resistance of the Nb-containing alloy was also enhanced as Nb is believed to accelerate the formation of a defect-free Cr₂O₃ scale. Overall, both developmental alloys, with and without the addition of Nb, were found to exhibit superior properties than RR1000.     

γ′ Precipitation Study of a Co-Ni-Based Alloy

A Co-Ni-based alloy strengthened by γ′-(L1₂) precipitates was utilized to investigate the precipitation evolution after various cooling rates and several aging conditions. In this study, the precipitate size and volume fraction have been studied via scanning electron microscopy and transmission electron microscopy. The influence of the precipitation evolution was measured via microhardness tests. The cooling rate study shows a more sluggish γ′ precipitation reaction compared to that observed in a Ni-based superalloy. Following a rapid cooling rate, the application of appropriate double aging treatments allows for the increase of the γ′ volume fraction as well as the control of the size and distribution of the precipitates. The highest hardness values reach those measured on supersolvus cast and wrought Ni-based superalloys. The observed γ′ precipitation behavior should have implications for the production, the heat treatment, the welding, or the additive manufacturing of this new class of high-temperature materials.     

On the Influence of Nb/Ti Ratio on Environmentally-Assisted Crack Growth in High-Strength Nickel-Based Superalloys

The effect of Nb/Ti ratio on environmentally-assisted crack growth of three prototype Ni-based superalloys is studied. For these alloys, the yield strength is unaltered with increasing Nb/Ti ratio due to an increase in grain size. This situation has allowed the rationalization of the factors influencing damage tolerance at 700 °C. Primary intergranular cracks have been investigated using energy-dispersive X-ray spectroscopy in a scanning transmission electron microscope and the analysis of electron back-scatter diffraction patterns. Any possible detrimental effect of Nb on the observed crack tip damage due to Nb-rich oxide formation is not observed. Instead, evidence is presented to indicate that the tertiary γ′-precipitates are dissolving ahead of the crack consistent with the formation of oxides such as alumina and rutile. Our results have implications for alloy design efforts; at any given strength level, both more and less damage-tolerant variants of these alloys can be designed.     

Enabling Large Superalloy Parts Using Compact Coprecipitation of γ′ and γ′′

Next-generation gas turbines will require disk materials capable of operating at 923 K (650 °C) and above to achieve efficiencies well beyond today’s 62 pct benchmark. This temperature requirement marks a critical turning point in materials selection. Current turbine disk alloys, such as 706 and 718, are limited by the stability of their major strengthening phase, γ′′, which coarsens rapidly beyond 923 K (650 °C) resulting in significant degradation in properties. More capable γ′ strengthened superalloys, such as those used in jet engine disks, are also limited due to the sheer size of gas turbine hardware; the γ′ phase overages during the slow cooling rates inherent in processing thick-section parts. In the present work, we address this fundamental gap in available superalloy materials. Through careful control of Al, Ti, and Nb levels, we show that fine (<100 nm) γ′ and compact γ′/γ′′ coprecipitate structures can be formed even under extremely slow cooling rates from high temperature. The presence of Ti is shown to have a dominant effect on phase formation, dictating whether γ′, γ′/γ′′ coprecipitates, or other less desirable acicular phases form on cooling. Sensitivity to cooling rate and aging heat treatment is also explored. A custom phase field model along with commercial precipitation kinetics software is used to better understand the phase evolution and stability of compact coprecipitates. The alloying strategies discussed here enable a new class of superalloys suitable for applications requiring large parts operating at high temperature.     

一种高铬的铁镍基高温合金物理化学相分析

采用物理化学相分析方法研究了高铬的铁镍基高温合金时效后碳化物和金属间化合物的析出行为,通过实验确定了铁镍基高温合金中析出相的萃取方法、相分离方法、钢中析出相的类型和含量、γ′相的粒度分布。研究结果表明,铁镍基高温合金中析出相为γ′、NbC、TiC、Laves和σ,随着时效时间的增加,NbC和TiC相含量变化不大,Laves相和γ′含量略有增加,σ相含量增加比较明显,γ′相的粒度随时效时间明显增加,σ相含量的增加和γ′相颗粒的增大是造成合金高温屈服强度下降的主要原因。研究结果对高铬的铁镍基高温合金成分的控制、生产工艺的选择和热处理制度的合理制定具有指导意义。     

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.     

Aging behavior of Fe-30 Ni alloys containing niobium

A study has been made of the precipitation reactions in Fe-30 wt pct alloys containing up to 5 wt pct Nb. The as-quenched structures of these alloys consist, of austenite, martensite in twinned as well as in massive form, and Ni₃Nb and Fe₂Nb precipitates. On aging at 700° and 800°C the main precipitation reaction results in the formation of hexagonal Laves phase Fe₂Nb, but Ni₃Nb in both bct and orthorhombic structures also precipitates. The precipitation of Fe₂Nb is a heterogeneous process and results in a considerable increase in the hardness of the alloy.     

钛质量分数对LF2合金微观组织与性能的影响

 采用热力学计算软件对LF2合金中的析出相进行计算,采用扫描电子显微镜、透射电子显微镜、微细相分析以及拉伸试验,对不同钛质量分数的LF2合金的微观组织和力学性能进行了研究,结果表明：LF2合金中γ′相以近球形在晶内弥散析出,尺寸约为20 nm,Laves相在晶界以纤维状和块状析出;随钛质量分数增加,γ′相数量增加,钛质量分数增加了0.92%,γ′相的质量分数是原来的1.35倍;Laves相数量增多,由纤维状变为短棒状。随钛质量分数增加,LF2强度增加,γ′相强化效果相对减弱,但γ′相仍然是最主要的强化相。     

Al含量对镍基单晶高温合金组织 和持久性能的影响

采用选晶法在定向凝固炉中制备了5.6 % Al和6.0 % Al的2种单晶高温合金,保持其它合金元素含量相同,热处理后在1 040 ℃长期时效800 h,采用扫描电镜研究了Al含量对合金共晶含量、热处理组织、长期时效组织和持久性能的影响.结果表明,随着Al含量增加,合金铸态组织中的共晶含量稍有增加,热处理组织中枝晶干γ′相无明显变化,枝晶间的γ′相稍有增大.随着Al含量增加,合金时效组织中TCP相析出量增加,枝晶间γ′相筏排化倾向增加,合金的组织稳定性变差.随着Al含量增加,合金的持久寿命增加,延伸率和断面收缩率减小.      

Effect of Co on Discontinuous Precipitation Transformation with TCP Phase in Ni-based Alloy Containing Re

The effect of Co on discontinuous precipitation (DP) transformation involving the formation of topologically close-packed (TCP) phase was investigated in three Ni-Cr-Re model alloys containing different levels of Co. One typical TCP phase, σ, was generated within DP cellular colonies along the migrating grain boundaries in experimental alloys during aging treatment. As a result of the increased solubility of Re in the γ matrix and enlarged interlamellar spacing of σ precipitates inside of growing DP colonies, Co addition suppressed the formation of σ phase and associated DP colonies. This study suggests that Co could potentially serve as a microstructural stabilizer in Re-containing Ni-base superalloys, which provides an alternative method for the composition optimization of superalloys.     

The influence of applied stress and stress sense on grain boundary precipitate morphology in a nickel-base superalloy during creep

Creep induced instability of strengthening precipitates at grain boundaries is of general concern in the applications of many high temperature alloys. Having shown that the general validity of the existing mechanism for such an instability in nickel-base superalloys may be considered suspect, this paper reports and discusses the effects of both tensile and compressive creep on γ′ grain boundary precipitate morphology in an alloy consisting of γ′ (Ni₃Al) precipitates in a γ (nickel solid solution) matrix. We find that the uniform distribution of γ′ precipitates is altered by the application of uniaxial creep stress, with the stress-induced precipitate morphology depending strongly on stress sense. Tensile creep results in the dissolution of γ′ precipitates at grain boundaries aligned more or less transverse to the stress axis, with an accompanying increase in volume fraction of γ′ precipitates at grain boundaries oriented parallel to, or almost parallel to the stress axis. In contrast, the reverse change in morphology occurs during compressive creep. The observed morphology changes and their dependence on stress sense are shown to be consistent with the flow of chromium atoms from grain boundaries that are under normal compression towards grain boundaries that are under normal tension. The results conclusively demonstrate that Herring-Nabarro type diffusion in multiphase, polycrystalline alloys can cause chemical changes in grain boundary regions which, in the extreme, result in phase changes at grain boundaries. The results and proposed mechanism are discussed in terms of the findings of other investigations.     

Effect of Compositional Changes of Laves Phase Precipitate on Grain Boundary Embrittlement in Long-Term Annealed 9 Pct Cr Ferritic Steel

In 9 to 12 pct chromium steels, the high-temperature mechanical properties are known to be strongly dependent on the formation and coarsening of Laves phase precipitates at boundaries. During high-temperature deformation, the Laves phase precipitate coarsening to over a critical size has been considered to trigger cavity formation at the precipitate-matrix interfaces. This coarsening, accompanied by the diffusion of W, Mo, and Cr, should change the mechanical properties and chemical composition of both Laves phase precipitates and the matrix. In this study, we aimed to clarify the effects of compositional changes of Laves phase precipitates on cavity formation during coarsening. The values of the Fe/Cr and W/Mo ratios in Laves phase precipitates were shown to induce different levels of strain energy in the vicinity of the Laves phase precipitate, consequently promoting the formation of cavities. Therefore, the compositional change of Laves phase precipitates was found to play a critical role in the grain boundary embrittlement of high Cr steel at elevated temperature.

     

Elemental Partitioning Characteristics of Equilibrium Phases in Inconel 718 Alloy at 600-1100 ℃

 The optimization of heat treatment and chemical composition for Inconel 718 alloy has been investigated uninterruptedly because of its excellent mechanical properties and metallurgical workability. The species, chemical compositions and content of equilibrium phases of Inconel 718 alloy in the temperature range of 600-1100 ℃ were calculated by using thermodynamic software “Thermo-Calc” and the latest relevant datebase of Ni-base superalloys. A concept of elemental partitioning fraction was used to study the partitioning characteristics of alloying elements in each equilibrium phase at different temperatures, such as Ni, Cr, Fe, Nb, Mo, Al, Ti and C, and some calculation results were confirmed under a scanning transmission electron microscope (STEM). The results showed that the elemental partitioning characteristics with the change of temperature revealed the selective partitioning characteristic of alloying elements in equilibrium phases at different temperatures, such as Nb was mainly distributed in δ and γ′ phase, C in carbides, Al and Ti in γ′ phase and Cr, Mo in Laves phase. At the same time, the effect of the change of component and quantity for each precipitated phase on matrix phase can be helpfully understood, which provided a theoretic foundation to optimize the chemical composition and heat treatment in different environments for Inconel 718 alloy.     

Iron Aluminium Alloys with Strengthening Carbides and Intermetallic Phases for High‐Temperature Applications

An overview of materials developments of iron aluminium alloys with strengthening precipitate phases is given. The discussion is focussed on recent studies on Fe‐Al‐based alloys with strengthening precipitates, such as κ‐phase Fe₃AlC_x, MC‐carbide and Laves phase. Alloys of the following alloy systems were investigated: Fe‐Al‐C, Fe‐Al‐Ta, Fe‐Al‐Ni, Fe‐Al‐Ti‐Nb, and Fe‐Al‐M‐C (M = Ti, V, Nb, Ta). The investigations were centred on microstructure, constitution, and mechanical properties of such Fe‐Al‐based alloys with Al contents ranging from 10 to 30 at. %. Mechanisms and problems are discussed and perspectives are outlined.     

Phase-Field Simulation of D019-Co3W Precipitation in Co–Al–W Superalloys

Metallurgical and Materials Transactions A - The γ′-Co3(Al, W) precipitates embedded in the γ matrix are a preferred morphology in Co–Al–W superalloys, while the stable...     

Simulation of effect of Nb and V on precipitated phases in 1Cr16Co5Ni2Mo1WVNbN steel

Thermo- Calc software was used to simulate the equilibrium precipitates in the 1Cr16Co5Ni2Mo1WVNbN steel at 650??, and the effect of Nb and V contents on precipitated phases in the steel was investigated. The calculation results show that the main equilibrium precipitates in steel are Laves phase, M23C6, MX and Z phase. With the increase of Nb content, the precipitation of MX phase increases significantly, while the amount of M23C6 carbids decreases, Laves phase increases slightly, the precipitation of Z phase decreases slightly. With the increase of V content, the precipitation of MX phase increases slowly, the amount of M23C6 carbides reduces slightly. There is no V element contained in Laves phase, and the increase of V content has little effect on the precipitation of Laves phase, precipitation of Z phase decreases slightly. The Nb and V contents have little effect on the precipitation temperature of M23C6, MX and Laves phase, and the starting precipitation temperature of Z phase decreases with the increase of Nb content, but increases with the increase of V content.     

Comparison of Thermodynamic Predictions and Experimental Observations on B Additions in Powder-Processed Ni-Based Superalloys Containing Elevated Concentrations of Nb

Boron additions to Ni-based superalloys are considered to be beneficial to the creep properties of the alloy, as boron has often been reported to increase grain boundary cohesion, increase ductility, and promote the formation of stable boride phases. Despite the importance, it is not well understood whether these improvements are associated with the presence of elemental boron or stable borides along the grain boundaries. In this investigation, two experimental powder-processed Ni-based superalloys containing elevated levels of Nb were found to exhibit increased solubility for B in the γ matrix when compared to similar commercial Ni-based superalloys. This resulted in an overall lower B concentration at grain boundaries that suppressed boride formation. As the predictive capability of CALPHAD database models for Ni-based superalloys have improved over the years, some discrepancies may still persist around compositionally heterogeneous features such as grain boundaries. Improved quantification of the characteristic partitioning of B as a function of the bulk alloy composition is required for understanding and predicting the stability of borides.     

Nano-/Ultrafine Eutectic in CoCrFeNi(Nb/Ta) High-Entropy Alloys

The development of single-phase high-entropy alloys (HEAs) emerges as a new paradigm shift in material research society during the last decade. A strong rise in the demand for structural and functional applications leads to the design and fabrication of super-strong eutectic HEAs through solidification processing. We report on the evolution of eutectic microstructure in CoCrFeNiNb_0.5 and CoCrFeNiTa_0.4 HEAs synthesized by arc melting. The evolved microstructure consists of nanolamellae of FCC γ-Ni and hexagonal β (Fe₂Nb or Co₂Ta type) Laves phases of 150 nm lamellae thickness. These alloys exhibit high yield strength of 2 GPa, ultimate compressive strength up to 2.2 GPa and 20% plastic strain. The strain rate jump test and transmission electron microscopic studies of deformed specimens have been performed to explore the microscopic mechanism of deformation in these high-strength advanced eutectic alloys.     

Al1.5Co4Fe2CrCux高熵合金的电磁吸波性能

高熵合金由于其在恶劣环境中的适用性以及对电磁场的多种衰减机制,使其在吸波领域具有巨大的潜在优势和广阔的应用前景。因Cu元素具有优异的延展性和导电性而被广泛应用,添加Cu元素以探究不同Cu含量下Al_1.5Co₄Fe₂CrCu_x (x=0.5, 1.0, 1.5, 2.0;摩尔比)高熵合金的吸波性能。结果表明,通过机械合金化制备的Al_1.5Co₄Fe₂CrCu_x高熵合金为片状、粒状和椭球状,具有软磁特性;饱和磁化强度随着Cu含量的增大逐渐减小,矫顽力则逐渐增大;同时,添加Cu元素有助于形成大长径比的粉末颗粒,调节合金粉末的磁性能和电磁性能,进一步增强合金粉末的介电损耗能力。当x=1.0时,Al_1.5Co₄Fe₂CrCu高熵合金粉末具有最高的衰减系数,在1.50 mm的较薄厚度下其最小反射损耗为-16.50 dB, 1.70 mm厚度下其在Ku波段的有效...