The Role of Refractory Metal Additions in Precipitation Processes in Superalloys

Abstract

Superaltoys are multi-component alloys containing many alloying additions developed for high temperature applications. Refractory metals are added to impart beneficial properties to the alloy. The role refractory metal additions in precipitation processes in superalloys are discussed in this paper. The minor variation in the alloying additions on the changes in precipitation behaviour are illustrated with the example of Alloy 718 and Alloy 625.     

合金元素Mo对钛合金相析出行为的影响

钛合金的相变过程中伴随着复杂多变的析出相,不同组织结构的析出相导致合金具有不同的机械性能。添加合金元素可以人为地控制钛合金中相的析出行为,但由于合金元素种类众多,合金元素对钛合金析出行为影响的机理有待进一步探讨研究。综述了合金元素Mo对钛合金析出行为影响的研究现状,以析出相的形态和尺度为主要考察对象,归纳总结了在α型、α+β型以及β型钛合金中添加Mo元素对析出相作用的机理,并指出了目前研究过程中存在的不足,希望为以后的钛合金析出行为的研究提供帮助。     

The role of nickel,copper, and columbium (Niobium) in strengthening a low-carbon ferritic steel

The contributions of the alloying elements nickel, copper, and columbium are evaluated in a low-carbon precipitation hardenable ferritic steel. The influences of nickel, copper, and columbium as individual and dual elemental additions on microstructure and mechanical properties are described. These elements each contribute to the as-rolled strength by grain refinement and solid solution strengthening. Copper provides an additional strength increment of about 15,000 psi as a precipitation hardener upon 1050°F aging.     

Spangle formation in galvanized sheet steel coatings

Very large grains, termed “spangles,” are produced on galvanized sheet steel coatings when lead is added to the zinc bath. The spangles have been attributed to melt undercooling prior to solidification. The present results indicate this is not the case, undercooling being less than 1 °C. The spangle diameter is shown to be dependent on the alloy addition to the bath, large spangles being obtained with Bi and Sb as well as Pb. The spangle size is related to the surface tension of the alloying addition, the size decreasing as the melt vapor surface tension of the alloying element increases. It is proposed that spangles form dendritically from a nucleus in the melt. Alloy additions with low interfacial energies and very limited solid solubility are highly concentrated ahead of the dendrite tip. This decreases the tip radius and increases the dendrite velocity, producing large grains. The basal plane orientation of the samples varies between 17 and 80 deg with respect to the steel sheet surface, which is inconsistent with basal plane dendritic growth in Zn along (1010) directions. It is proposed that solute additions to the melt and growth in a thin liquid layer can modify the dendrite growth direction, accounting for the spangle orientation. On leave from Obafemi Awolowo University, lie Ife, Oyo State, Nigeria     

Cu-Precipitation Strengthening in Ultrahigh-Strength Carburizing Steels

Ultrahigh hardness levels greater than 700 VHN can be obtained in secondary hardening carburizing steels but depend on costly Co alloying additions to maximize hardness achieved through M₂C-type carbide precipitation strengthening. This study aims to incorporate nanometer-scale bcc Cu precipitates to both provide strength as well as catalyze M₂C nucleation in the absence of or with reduced Co. Cu additions of 1.0 and 3.7?wt pct were investigated, using a series of mechanistic models coupled with thermodynamic computational tools to derive final compositions. Thirty-pound experimental heats were cast of each designed alloy, samples of which were carburized and tempered to determine their hardness response. Characterization revealed the successful incorporation of Cu alloying additions into this family of steels, demonstrating a secondary hardening response even in the absence of Co. Matrix strength levels were close to those predicted by design models; however, all four alloys demonstrated a hardness deficit of approximately 200 VHN at the carburized surface, suggesting recalibration of the M₂C precipitation strengthening model may be required in these alloys.     

Microstructural development in high volume fraction gamma prime Ni-base oxide-dispersion-strengthened superalloys

The mechanical alloying process has successfully combined oxide-dispersion-strengthening with conventional gamma prime precipitation hardening for advanced gas turbine materials. INCONEL* alloy MA 6000, a mechanically alloyed Ni-base superalloy, has the highest temperature capability among commercially available superalloys. Further improvement of the intermediate temperature strength has been pursued by both increasing the gamma prime content up to 80 vol pct and controlling the additions of refractory metals. The microstructural development of these new experimental alloys is reported in this paper, especially for an alloy, nominally identified as Alloy 51, having the composition Ni-9.3 pct Cr-8.5 pct Al-6.6 pct W-3.4 pct Mo-0.15 pct Zr-0.01 pct B-l.l pct Y₂O₃ (wt pct). Both the primary and the secondary recrystallized microstructures of the alloy were characterized in terms of gamma grain structure, gamma prime precipitate morphology, orientation relationships, dispersoids, carbide/nitride particles, and chemical composition of intermetallic phases. The microstructural stability of the alloy under stress rupture conditions was also investigated in terms of coarsening/coalescence of gamma prime precipitates. Correlation of the microstructural information with the high temperature properties of the alloy is also briefly discussed. Formerly with the INCO R&D Center, Suffern, NY.     

Characterization by thermoelectric power of a commercial aluminum-iron-silicon alloy (8011) during isothermal precipitation

We have characterized a commercial 8011 (Al-Fe-Si) alloy by studying samples under different initial states of strain hardening and iron and silicon supersaturation using thermoelectric power as a measurement technique. Isothermal kinetics of precipitation are obtained in the temperature range between 225 °C and 600 °C. We determine the atom fraction precipitated for each microstructural condition, identifying the dominant alloying additions and evaluating the typical parameters of the precipitated phases, such as, for example, the apparent activation energy. Finally, we determine the time-temperature-transformation (TTT) diagrams. Our results prove that iron is the alloying addition that controls the precipitation kinetics of the 8011 alloy in the temperature range studied.     

Effect of Ti Additions on Micro‐Alloyed Nb TRIP Steel

In the present study, the influence of Ti‐additions on the mechanical properties of Nb‐microalloyed TRIP steel is investigated. Ti micro‐alloying additions to multi‐phase Nb TRIP steel result in a substantial increase of the yield strength and a reduction of strain hardening. The increase of the yield strength can be attributed mainly to grain refinement with a relatively small contribution of precipitation hardening. Based on general principles and well‐known models of alloying strengthening, metallurgical reasons for the observed mechanical behavior of the steel can be formulated. The contribution of precipitation hardening is relatively small as Ti‐addition result in the formation of coarse (Nb,Ti)(C,N) particles. The addition of Ti to a Nb‐microalloyed TRIP steel leads to a pronounced enhancement of precipitation kinetics of (Nb,Ti)(C,N), thereby increasing their phase fraction. The precipitates coarsen and tend to form groups of aggregates of particles rather than single isolated particles with increasing intercritical annealing time. In addition, Ti‐addition to Nb‐microalloyed TRIP steel has a direct influence on the chemical composition of the precipitates, which become Ti‐rich.     

Stabilization of thermosolutal convective instabilities in Ni-based single-crystal superalloys: Carbide precipitation and rayleigh numbers

The influence of carbide precipitation on grain-defect formation during unidirectional solidification of experimental single-crystal Ni-based superalloys has been assessed over a wide range of compositions with large variations in Re, W, and Ta. In all instances, carbon additions of up to 0.15 wt pct were determined to be statistically significant with respect to stabilizing against the formation of grain defects, such as freckle chains, during solidification. Assessment of the segregation behavior of the constituent alloying additions via a Scheil-type analysis enabled estimation of critical Rayleigh numbers denoting the onset of thermosolutal convection. Precipitation of Ta-rich MC carbides near the liquidus temperature of the alloy was found to interact strongly with the mechanisms associated with freckle formation. Segregation analyses and phase-transformation temperature measurements were used to assess the corresponding Rayleigh numbers for the experimental alloys and to modify the Rayleigh criterion to account for carbide precipitation. Mechanisms pertaining to the interaction of carbides with the onset of thermosolutal convection are discussed.     

Retardation of intermetallic phase formation in experimental superferritic stainless steels

While superferritic stainless steels containing 29 pct chromium possess excellent resistance to corrosion, they may, under certain conditions, be embrittled by the precipitation of intermetallic phases. The extent to which the precipitation reactions can be retarded by alloying additions of aluminum and copper has been evaluated. It was found that additions of aluminum to an Fe-29 pct Cr-4 pct Mo-1.5 pct Ni base alloy suppress the precipitation of the undesirable sigma and chi intermetallic phases, but additions of up to 3 pct aluminum promote 475 ‡C embrittlement. Additions of copper slightly reduce the precipitation of sigma and chi phases under most conditions but enhance 475 ‡C embrittlement. The resistance to corrosion in 10 pct H₂SO₄ and 10 pct FeCl₃ was assessed. All the aluminum-containing alloys performed significantly better in H₂SO₄ than the base alloy; however, large additions of aluminum had a deleterious effect on the pitting resistance in FeCl₃. Additions of copper improved the resistance to FeCl₃ and lowered the rate of corrosion in the H₂SO₄ solution used.     

A melting and solidification study of alloy 625

The melting and solidification behavior of Alloy 625 has been investigated with differential thermal analysis (DTA) and electron microscopy. A two-level full-factorial set of chemistries involving the elements Nb, C, and Si was studied. DTA results revealed that all alloying additions decreased the liquidus and solidus temperatures and also increased the melting temperature range. Terminal solidification reactions were observed in the Nb-bearing alloys. Solidification microstructures in gastungsten-arc welds were characterized with transmission electron microscopy (TEM) techniques. All alloys solidified to an austenitic (γ) matrix. The Nb-bearing alloys terminated solidification by forming various combinations of γ/MC(NbC), γ/Laves, and γ/M₆C eutectic-like constituents. Carbon additions (0.035 wt pct) promoted the formation of the γ/MC(NbC) constituent at the expense of the γ/Laves constituent. Silicon (0.4 wt pct) increased the formation of the yJLaves constituent and promoted formation of the γ/M₆C carbide constituent at low levels (<0.01 wt pct) of carbon. When both Si (0.4 wt pct) and C (0.035 wt pct) were present, the γ/MC(NbC) and γ/Laves constituents were observed. Regression analysis was used to develop equations for the liquidus and solidus temperatures as functions of alloy composition. Partial derivatives of these equations taken with respect to the alloying variables (Nb, C, Si) yielded the liquidus and solidus slopes t(m _L , m _S ) for these elements in the multicomponent system. Ratios of these liquidus to solidus slopes gave estimates of the distribution coefficients (k) for these same elements in Alloy 625.     

钒和钼对微合金化贝氏体钢第二相析出的影响

利用热模拟试验机Gleeble - 3800,热模拟试验研究了V、Mo、V+Mo等元素、加热温度、保温时间对微合金化贝氏体钢中第二相析出的影响.结果表明,Nb、V、Ti、Mo的复合加入有利于第二相的析出,加热温度和保温时间对析出量的影响较小.     

Molybdenum in Nb-C alloys

The effects of molybdenum alloying additions to niobium on the carbide phases and their precipitation behavior were investigated. The experimental alloys included Nb-0.1C, Nb-15Mo-0.1C, and Nb-30Mo-0.1C. After selected heat treatments the microstructural changes were determined by metallography and the carbide phases were extracted and identified by X-ray diffraction and chemical analysis. The results are essentially in agreement with recent phase diagram determinations. Additions of 30 wt pct Mo appears to slightly increase the solubility of carbon in niobium at temperatures around 1650°C. The solubility of molybdenum in Nb₂C is very small. Discontinuous precipitation of β-Nb₂C was found to occur in the Nb-30Mo-0.1C alloy during annealing at 1200°C. The important, overall effect of molybdenum in Nb-C alloys is to decrease the rate of niobium carbide precipitation so that appreciable carbon supersaturation can be achieved even after comparatively slow furnace cooling.     

日本桑阿洛依公司的异型硬质合金生产

叙述了日本桑阿洛依公司异型硬质合金的生产方法。对该公司在混合料制备、成形加工和烧结等工艺方面的独特方法进行了较深入的探讨。     

Effect of alloying additions on secondary hardening behavior of Mo-containing steels

The effect of alloying additions on secondary hardening behavior in Fe-Mo-C steels has been investigated by means of the successive alloying additions of Cr, Co, and Ni. The Cr additions promote M₃C cementite formation. The Ni additions destabilize the cementite formation, while the Co additions retard dislocation recovery and present the necessary sites for M₂C formation which provides the secondary hardening. Professor Kwon is jointly appointed at the Center for Advanced Aerospace Materials.     

Effect of Mn,Si and Mn‐Si Alloying on the Precipitation of Ultra‐fine Oxides in Fe during Solidification

The effect of Mn, Si and Mn‐Si alloying on the precipitation of oxide inclusions in Fe during solidification has been investigated. The results show that the inclusions precipitating during solidification are relatively small and distribute uniformly in Mn, SI and Mn‐Si alloyed steels. Most of the inclusions are nearly spherical. The maximum diameter of inclusions is only 3.3μm in the three types of alloyed steels. The average size of inclusions is 1.3μm, 1.2μm and 1.1μm in Mn, Si and Mn‐Si alloyed steels, respectively. The maximum amount of inclusions is 1.1×10⁵ per unit volume (mm^?3) in Mn alloyed steel and the minimum is 5.8×10⁴ per unit volume in Si alloyed steel. The volume fractions of the inclusions with Mn, Si and Mn‐Si alloying are 0.01%, 0.005% and 0.006%, respectively.     

Discontinuous Precipitation and Phase Stability In Re- and Ru-Containing Nickel-Base Superalloys

The phase stability of nickel-base superalloys has been investigated using a new in-house-designed alloy series with stepwise increased additions of Re and Ru at otherwise fixed atomic fractions of alloying elements. Results presented in this study are focused on the lesser-known topologically closed packed (TCP) formation of columnar colonies or so-called discontinuous precipitation. A detailed investigation of these colonies allowed for identifying compositional changes during the growth process and for providing a three-dimensional (3-D) illustration of the TCP phases within these colonies. The results were used to compare the colony growth process with existing growth models. Furthermore, the influence of Re and Ru on the appearance of discontinuous precipitation has been investigated by means of colony width and the effect on creep properties. Larson-Miller plots are given to illustrate the creep strength of directionally solidified samples with and without TCP colonies compared with single crystalline samples free from TCP colonies.     

镍基高温合金GH4706析出相的热力学计算与分析

应用Thermo-Calc热力学计算软件,模拟元素含量及热处理温度对镍基高温合金GH4706平衡相析出规律的影响。结果表明:平衡析出相的种类和析出温度范围与微观组织观测和差热分析的实验结果基本一致。MC碳化物的初始析出温度随Nb、Ti含量增加而降低,而析出量主要受C含量影响;η相初始析出温度与析出量随Ti含量增加而增大,受Nb、Fe影响较小;γ'相初始析出温度与析出量随Al含量增加而升高,受Ti、Nb含量影响较小;合金凝固过程中Nb、Ti会产生显著正偏析,Cr产生负偏析;Nb、Ti含量增加提高合金初熔点,降低合金的终熔点,使凝固温度范围变窄。     

原子发射光谱法分析国防军工新材料——铝锂合金

介绍了国防军工新材料铝锂合金一种新的分析方法-原子发射光谱法,该方法用于炉前分析,结果准确而又快速简便以往在国内未见报道,用DV-4光电谱仪在西南铝加工厂近两年铝锂合金生产及标准样品研制分析实践中,找出最佳分析参数,建立了铝锂合金分析方法,所建立的校准曲线拟合系数,高基本在0.999以上,分析结果令人满意,经过与俄罗斯标样进行对比试验（国内无铝锂合金标样）,本方法的校准曲线拟合系数、精密度和准确度均已达到或超过在铝锂合金分析居世界领先水平的俄罗斯标样,本法填补了国内在用原子发射光谱法对铝锂合金进行炉前快速分析方面的空白。