Coarsening resistance of M2C carbides in secondary hardening steels: Part II. Alloy design aided by a thermochemical database

In high Co-Ni steels containing the strong carbide-forming elements Mo, Cr, and W, secondary hardening is accomplished by the precipitation of fine-scale M₂C alloy carbides. Thermodynamic stability and coarsening resistance of these carbides depend on the alloy content of these elements. A model for the M₂C coarsening kinetics in multicomponent alloys has been used to identify the optimum alloying addition for maximum coarsening resistance and as a basis for selection of four experimental alloy steels. Necessary information pertaining to the equilibrium in these steels was obtained using the Thermo-Calc software and database developed at the Royal Institute of Technology, Stockholm, Sweden.     

Coarsening resistance of M2C carbides in secondary hardening steels: Part I. Theoretical model for multicomponent coarsening kinetics

The development of very high-strength levels in many alloy steels is achieved by a secondary hardening reaction. In high Co-Ni steels containing the strong carbide-forming elements Mo, Cr, and W, secondary hardening is accomplished by the precipitation of fine-scale M₂C alloy carbides. Coarsening resistance of the M₂C precipitates depends on the alloy content of these elements, and there should be an addition to the alloy of these carbide-forming elements which optimizes the M₂C coarsening resistance. Current Lifshitz-Slyozov-Wagner (LSW) theory^[2,3] cannot properly be used to describe, the coarsening behavior of multicomponent carbides, which involves concentrations and diffusivities of two or more solutes and nonspherical carbide morphologies. A model is introduced for the coarsening resistance of multicomponent carbides. This model treats the coarsening of shape-preserving particle and is applicable to rodlike particles.     

M2C precipitates in isothermal tempering of high Co-Ni secondary hardening steel

The effects of isothermal tempering on the coarsening behavior of hexagonal M₂C precipitates and the secondary hardening reaction in ultrahigh-strength AerMet 100 steel were investigated. The tempering temperatures were 468 °C, 482 °C, and 510 °C, and the tempering time spanned the range from 1 to 400 hours. Experimental studies of the coarsening behavior of the carbides were made by utilizing transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray diffractometry (XRD). The hardness at the secondary hardening peak was about HRc 55. The average length and diameter of M₂C carbides were 4 to 8 nm and 1.5 to 2.5 nm, respectively, at all three tempering temperatures; hence, the aspect ratio was almost 3, an equilibrium value in this case. The size of the M₂C carbides increased monotonically with time, but the growth kinetics did not exactly follow the classical coarsening behavior. The amount of precipitated austenite increased with tempering time and temperature. M₂C precipitates were still relatively fine even after 200 hours of tempering. This feature seemed to be closely related to the high hardness maintained after prolonged tempering.     

Effect of Silicon on Carbide Precipitation after Tempering of H11 Hot Work Steels

The formation of secondary carbides during tempering of H11 hot work steels at 898 K (625 °C) was studied by transmission electron microscopy (TEM) and related to the previously established effects of Si content on mechanical properties. Lower Si contents (0.05 and 0.3 pct Si) and higher Si contents (1.0 and 2.0 pct Si) were observed to yield different carbide phases and different particle distributions. Cementite particles stabilized by Cr, Mo, and V in the lower Si steels were found to be responsible for similar precipitation hardening effects in comparison to the M₂C alloy carbides in the higher Si steels. The much higher toughness of the lower Si steels was suggested to be due to a finer and more homogeneous distribution of Cr-rich M₇C₃ carbides in the interlath and interpackage regions of the quenched and tempered martensite microstructure. The present effects of Si content on the formation of alloy carbides in H11 hot work steels were found to be the result of the retarding effect of Si on the initial formation of cementite, well known from the early tempering stages in low alloy steels.     

An analytical electron microscopy study of paraequilibrium cementite precipitation in ultra-high-strength steel

To support quantitative design of ultra-high-strength (UHS) secondary-hardening steels, the precipitation of cementite prior to the precipitation of the M₂C phase is investigated using a model alloy. The microstructure of cementite is investigated by transmission electron microscopy (TEM) techniques. Consistent with earlier studies on tempering of Fe-C martensite, lattice imaging of cementite suggests microsyntactic intergrowth of M₅C₂ (Hägg carbide). The concentration of substitutional alloying elements in cementite are quantified by high-resolution analytical electron microscopy (AEM) using extraction replica specimens. Quantification of the substitutional elements in cementite confirms its paraequilibrium (PE) state with ferrite at the very early stage of tempering. The implications of these results are discussed in terms of the thermodynamic driving force for nucleation of the primary-strengthening, coherent M₂C carbide phase. The ferrite-cementite PE condition reduces the carbon concentration in the ferrite matrix with a significant reduction of M₂C driving force. The kinetics of dissolution of PE cementite and its transition to other intermediate states will also influence the kinetics of secondary hardening behavior in UHS steels.     

The role of alloy composition in the precipitation behaviour of high speed steels

The role of alloy composition in determining the microstructure and microchemistry of a series of related high speed steels has been investigated by a combination of analytical electron microscopy and atom-probe field ion microscopy. The four steels which were investigated (M2, ASP 23, ASP 30 and ASP 60) cover a large range of C, V and Co contents. Excepting the Co content, the composition of primary MC and M₆C carbides and as-hardened martensite was similar in all four alloys and the major effect of increasing the content of C and V was to increase the volume fraction of MC primary carbides. Precipitation of proeutectoid carbides (mainly MC and M₂C) occurred during hardening of all four steels and the extent of this was greatest in the highly alloyed ASP 60. Tempering at 560°C resulted in the precipitation of extremely fine dispersions of MC and M₂C secondary carbides with very mixed compositions in all four steels. It was found that, as well as hindering the formation of autotempered M₃C in the as-hardened martensite, additions of Co refined the secondary carbide dispersion and delayed overaging reactions. Overaging at 600°C resulted in the precipitation of M₃C, M₆C and M₂₃C₆ at the expense of the fine MC and M₂C secondary carbide dispersion.     

Magnetic Nondestructive Evaluation of Creep Behavior in Water-Quenched Modified 9Cr-1Mo Steel

Water-quenched modified 9Cr-1Mo steel was creep tested in the laboratory at a temperature of 600 °C and 125 MPa stress. Magnetic Barkhausen emissions (MBE) measurements were carried out by interrupting the test at different lengths of time. Creep damage in such steel was observed by an increase in root mean square (RMS) voltage of the MBE. The magnetic softening was corroborated with the decrease in pinning density in the material for the coarsening of carbides (M₂₃C₆) and formation of massive phases (Fe₂Mo), which comes at the expense of a large number of finer carbides. Before failure, the rate of increase in RMS voltage of the MBE decreased due to the demagnetizing field offered by the massive phases. The microstructural analysis was carried out using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) study.     

Effect of Heat Treatment on Microstructure and Mechanical Properties of 2.25Cr–1Mo Steel

The effect of heat treatment on microstructure and mechanical properties of a ferritic heat‐resistant steel, 2.25Cr–1Mo, was investigated. The characteristics of carbides, i.e., size, morphology, distribution, and composition, in different stages of heat treatment were examined by using transmission electron microscopy (TEM) and energy dispersive X‐ray (EDX). As the heat treatment proceeded from normalizing and tempering (NT, the delivery state), simulated post‐welding heat treatment (PWHT), to step cooling (SC), the carbides evolved from M₃C, Mo₂C to M₇C₃, M₂₃C₆. The uniformly dispersed carbides, e.g., Mo₂C, M₇C₃, and M₂₃C₆, are responsible for the excellent mechanical properties and creep resistance of the steel. The result demonstrates that the coarsening of carbides deteriorates impact toughness and the morphology, crystal structure, and chemical composition of carbides are also important influencing factors.     

How TEM Projection Artifacts Distort Microstructure Measurements: A Case Study in a 9 pct Cr-Mo-V Steel

Morphological data obtained from two-dimensional (2D) and three-dimensional (3D) transmission electron microscopy (TEM) observations were compared to assess the effects of TEM projection errors for submicron-size precipitates. The microstructure consisted of M₂₃C₆ carbides in a 9 pct Cr-Mo-V heat resistant steel before and after exposure to creep conditions. Measurements obtained from about 800 carbides demonstrate that particle size and spacing estimates made from 2D observations overestimate the more accurate values obtained from 3D reconstructions. The 3D analysis also revealed the M₂₃C₆ precipitates lengthen anisotropically along lath boundary planes, suggesting that coarsening during the early stage of creep in this alloy system is governed by grain boundary diffusion.     

Carbide reactions (M3C→M7C3→M23C6→M6C) during tempering of rapidly solidified high carbon Cr-W and Cr-Mo steels

Carbide transformations of M₃C → M₇C₃ → M₂₃C₆ → M₆C and crystallographic relationships among these carbides were examined by transmission electron microscopy. Two kinds of high carbon-chromium steels containing tungsten or molybdenum were quenched rapidly from the melts and tempered at temperatures up to 700°C. By tempering at 600°C, M₇C₃ carbides nucleated mostly on cementite/ferrite interfaces and grew inward the cementite byin- situ transformation.In-situ transformations from M₇C₃ to M₂₃C₆ and from M₂₃C₆ to M₆C were also found in these alloy steels during tempering at higher temperatures. Mutual relationships of crystal orientations among M₃C, M₇C₃, M₂₃C₆ and M₆C were decided as follows: {fx739-01}.     

Grain growth and carbide precipitation in superalloy, UDIMET 520

The results of an experimental study on the grain coarsening behavior, M₂₃C₆ carbide precipitation, and secondary MC carbide precipitation kinetics in UDIMET 520 are presented. Primary MC carbides and M (C, N) carbonitrides strongly influence the grain growth, with their dissolution near 1190 °C and 1250 °C, respectively, resulting in two distinct grain coarsening temperatures (GCTs). M₂₃C₆ carbides precipitate in the alloy over a wide range of temperatures varying between 600 °C and 1050 °C. A discrete M₂₃C₆ grain boundary carbide morphology is observed at aging temperatures below 850 °C. Secondary MC carbides formed at temperatures ranging between 1100 °C and 1177 °C, in specimens in which primary MC dissolution had been obtained at solution treatment temperatures of 1190 °C to 1250 °C. A schematic time-temperature-transformation (TTT) diagram for understanding the microstructure and precipitation inter-relationships in UDIMET 520 alloy is also presented.     

Carbide Precipitation in 2.25 Cr-1 Mo Bainitic Steel: Effect of Heating and Isothermal Tempering Conditions

The effect of the tempering heat treatment, including heating prior to the isothermal step, on carbide precipitation has been determined in a 2.25 Cr-1 Mo bainitic steel for thick-walled applications. The carbides were identified using their amount of metallic elements, morphology, nucleation sites, and diffraction patterns. The evolution of carbide phase fraction, morphology, and composition was investigated using transmission electron microscopy, X-ray diffraction, as well as thermodynamic calculations. Upon heating, retained austenite into the as-quenched material decomposes into ferrite and cementite. M₇C₃ carbides then nucleate at the interface between the cementite and the matrix, triggering the dissolution of cementite. M₂C carbides precipitate separately within the bainitic laths during slow heating. M₂₃C₆ carbides precipitate at the interfaces (lath boundaries or prior austenite grain boundaries) and grow by attracting nearby chromium atoms, which results in the dissolution of M₇C₃ and, depending on the temperature, coarsening, or dissolution of M₂C carbides, respectively.     

Influence of tempering temperature on stability of carbide phases in 2.6cr-0.7mo-0.3v steel with various carbon content

The present work evaluates the influence of the bulk carbon content (0.1, 0.006, and 0.005 wt pct) and tempering temperature (823, 853, and 913 K) on stability, chemical composition, and size of carbide particles in 540 ks tempered states of 2.6Cr-0.7Mo-0.3V steel. The scanning transmission electron microscopy/energy-dispersive X-ray spectroscopy (STEM/EDXS) and electron diffraction methods were used to analyze the carbide particles. A characteristic energy-dispersive X-ray (EDX) spectrum can be attributed to each of the identified carbides. The MC carbide is stable in all experimental states. The phase stability of Fe-Cr-rich carbides increased in the order ε, Fe₃C → M₃C → M₇C₃, with tempering temperature increasing. In steels with higher carbon content tempered at low temperature, M₂₃C₆ carbide was also noted. The Mo₂C and M₆C carbides were not observed. It was shown that the decrease of the bulk carbon content has the same influence on the carbide phases stability as the increase of the bulk vanadium content at the unchanged Cr, Mo, C bulk contents and tempering temperature. Similarly, the decrease of tempering temperature has the same influence on the carbide phases stability as the decrease of the bulk Cr content at the unchanged V, Mo, and C bulk contents.     

Carbonitride precipitate growth in titanium/niobium microalloyed steels

Transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) have been used to investigate the morphology, distribution, composition, particle size distributions, and growth kinetics of carbonitride precipitates in steels containing low levels of Ti, Nb, C, and N. During the aging, only the complex carbonitride precipitates of the form (Ti_xNb_1−x) (C_yN_1-y) were found in the newly nucleated and growing particles. The youngest of these particles which approach the size of critical nuclei tends to be Ti-rich. Almost all of these particles are nearly spherical. The initial growth of the precipitates, which is very rapid, lasts less than 30 seconds followed by slow ripening. A model predicting the growth kinetics of carbonitrides and composition variation within the precipitates for the initial stage (before coarsening) has been developed based on equilibrium thermodynamics with the inclusion of capillarity and multicomponent diffusional kinetics. Satisfactory agreement with the experimental results has been demonstrated.     

Effect of molybdenum on the fracture characteristic of high-speed steel quenched matrix

The fractures of three model alloys, imitating by their chemical composition the matrixes of the quenched high-speed steels of various Mo: W relations were analyzed. According to the measurements of the stress intensity factor K_Ic and the differences in the precipitation processes of carbides it was found out that the higher fracture toughness of the matrix of the molybdenum high-speed steels than on the tungsten ones is the results of the differences in the kinetics of precipitation from the martensite matrix of these steels during tempering. After tempering at 250 and 650°C the percentage of the intergranular fracture increases with the increase of the relation of Mo to W in the model alloys of the high-speed steel matrix. This is probably the result of higher precipitation rate of the M₃C carbide (at 250°C) and the MC and M₆C carbides (at 650°C) in the privileged regions along the grain boundaries. The change of the character of the model alloy fractures after tempering at 450°C from the completely transgranular one in the tungsten alloy to the nearly completely intergranular one in the molybdenum alloy indicates that the coherent precipitation processes responsible for the secondary hardness effect in the tungsten matrix begin at a lower temperature than in the molybdenum matrix. After tempering for the maximum secondary hardness the matrix fractures of the high-speed steels reveal a transgranular character regardless the relation of Mo to W. The higher fracture toughness of the Mo matrix can be the result of the start of the coherent precipitation processes at a higher temperature and their intensity which can, respectively, influence the size of these precipitations, their shape and the degree of dispersion. The transgranular character of the fractures of the S 6-5-2 type high-speed steel in the whole range tempering temperatures results from the presence of the undissolved carbides which while cracking in the region of stress concentration can constitute flaws of critical size which form the path of easy cracking through the grains. The transgranular cracking of the matrix of the real high-speed steels does not change the adventageous influence of molybdenum upon their fracture toughness. On the other hand, the carbides, undissolved during austenitizing, whose size distribution in the molybdenum steels from the point of view of cracking mechanics seems to be unsatisfactory, influence significantly the fracture toughness of these steels.     

Primary Carbide Formation in Tool Steels: Potential of Selected Laboratory Methods and Potential of Partial Premelting for the Generation of Thermodynamic Data

To predict the solidification and product properties of tool steels with complex chemical compositions, an understanding of the transformation behavior is crucial. Therefore, the quaternary Fe–C system with 10 wt% Cr and 3 wt% W (a subsystem of cold work steels, with M₇C₃ and M₂₃C₆ carbides) and the Fe–C system with 6 wt% W and 5 wt% Mo (simplified high-speed steel, with M₆C and MC carbides) are selected. The motivation for this study is to develop a methodology for the safe and fast production of model alloys and the close to equilibrium performance of differential scanning calorimetry (DSC) measurements. Regular diffusion annealing of as-cast carbidic steels is time-consuming, but with an additional heat treatment during the DSC measurement in the semisolid zone (30–50% liquid phase fraction), a status close to equilibrium can be achieved within minutes due to the high diffusion. To prove the potential of the equilibration by partial premelting in the DSC, additional equilibration and quenching experiments are performed in a Tammann furnace and investigated using a scanning electron microscope and X-ray diffraction analysis. By combining these methods, carbide types and the transformation temperatures can be verified to evaluate and construct complete phase diagrams.     

Coarsening of M23C6 Precipitates in an Fe-Cr-C Ternary Alloy

 Coarsening of M23C6 precipitates in an Fe-12.4Cr-0.13C ternary alloy has been investigated ageing at 780 ℃ up to 200 h. Evolution of M23C6 carbides at different ageing times was determined experimentally using transmission electron microscopy. Particle size distribution was obtained with different measuring methods. Simulations of coarsening of M23C6 precipitates were carried out using computational thermodynamics and kinetics. Results showed low coarsening rates for M23C6 precipitates in the Fe-Cr-C ternary alloy. Interfacial energy of M23C6/ferrite interface is between 0.1 and 0.3 J·m-2 for the coarsening of M23C6 ageing at 780 ℃.     

Carbide Transformations during Aging of Wear-Resistant Cobalt Alloys

Wear-resistant cobalt-based alloys were thermally aged for 30, 300, and 1000 hours at 650°C and 850°C in vacuum sealed tubes of silica. Unidirectional solidification was used to promote coarser structures easier to investigate. The precipitates were characterized by scanning and transmission electron microscopy, X-ray diffraction, and microprobe analysis. During aging secondary M₂₃C₆ transforms into M₆C. Concomitantly, the primary carbides undergo internal transformation from M₇C₃ to M₆C, and M₆C loses carbon and becomes M₁₂C. Three main findings are reported: (1) a correlation between the nature of precipitates and the chemical segregations, (2) modification of the composition, the morphology, and the crystallographic structure of the carbides, and (3) in these alloys M₂₃C₆ is only an intermediate phase thermodynamically unstable.     

Three-Dimensional (3-D) Atom Probe Tomography of a Cu-Precipitation-Strengthened, Ultrahigh-Strength Carburized Steel

In an effort to reduce material cost, experimental steel alloys were developed that incorporated Cu precipitation in lieu of costly Co alloying additions in secondary hardening carburizing gear steels. This work utilizes three-dimensional atom probe tomography to study one of these prototype alloys and quantify the nanoscale dispersions of body-centered cubic (bcc) Cu and M₂C alloy carbides used to strengthen these steels. The temporal evolution of precipitate, size, morphology, and interprecipitate interactions were studied for various tempering times. Findings suggest that Cu precipitation does act as a catalyst for heterogeneous nucleation of M₂C carbides at relatively high hardness levels; however, the resultant volume fraction of strengthening carbides was noticeably less than that predicted by thermodynamic equilibrium calculations, indicating a reduced potency compared with Co-assisted precipitation. Microstructural information such as precipitate size and volume fraction was measured at the peak hardness condition and successfully used to recalibrate alloy design models for subsequent alloy design iterations.     

Crystallography and Morphology of MC Carbides in Niobium-Titanium Modified As-Cast HP Alloys

The microstructures of two as-cast heats of HP alloy stainless steels modified with niobium and titanium were examined with particular attention paid to the interdendritic niobium-titanium-rich carbides formed during solidification of these alloys. Generally, these precipitates obtain a blocky morphology in the as-cast condition. However, the (NbTi)C precipitates may obtain a nodular morphology. To provide further insight to the origin of the two different morphologies obtained by the (NbTi)C precipitates in the HP-NbTi alloy, the microstructure and crystallography of each have been studied in detail using scanning electron microscopy, transmission electron microscopy, various electron diffraction methods (EBSD, SAD, and CBED), and energy-dispersive X-ray spectroscopy.