Coarsening resistance of M2C carbides in secondary hardening steels: Part III. Comparison of theory and experiment

A model for the coarsening resistance of multicomponent carbides was used to study the effect of Mo and Cr on the coarsening kinetics of M₂C carbides in commercial AF1410 and experimental alloy steels. Experimental studies of coarsening behavior of the carbides in these steels have been made by using transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The measured coarsening rate constant agrees with model predictions within a factor of 2 to 3. The coarsening kinetics of M₂C carbides in these alloys is found to be controlled by the volume diffusion of alloying element M. A Cr-Mo alloy steel with the predicted optimum composition showed the slowest coarsening kinetics and highest hardness at long tempering times.     

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.     

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.     

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.     

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.     

Precipitation reactions during the heat treatment of ferritic steels

The precipitation reactions in two ferritic steels, 9Cr-lMo-V-Nb and 12Cr-lMo-V-W, were studied. Analytical electron microscopy, optical microscopy, electrolytic extractions, and hardness measurements were used to determine the types, amounts, and effects of precipitates formed as a function of the heat treatment. The effect of variations in the austenitizing treatment was ascertained. In addition to variations in the austenitizing time and temperature, different cooling rates after austenitization were also used. Air cooling after austenitization (normalization) resulted in little precipitation in both alloys. Precipitation in the 12Cr-lMo-V-W alloy after furnace cooling was found in all cases examined. Under certain conditions precipitation was also found after furnace cooling the 9Cr-lMo-V-Nb alloy. However, when compared to the amount of precipitate in the fully tempered state, the 9Cr-lMo-V-Nb showed a much greater variation in the degree of precipitation following furnace cooling. In addition, the matrix microstructure of the 9Cr-lMo-V-Nb alloy was very sensitive to cooling rate. The precipitation reactions during tempering after a normalizing treatment were followed as a function of tempering treatment. Tempering temperatures were varied from 400 to 780 °C. The carbide precipitation was essentially complete after one hour at 650 °C for both alloys. Analytical microscopy was used to identify the precipitates. In the 9Cr-lMo-V-Nb alloy, a combination of chromium-rich M₂₃C₆ and vanadium-niobium-rich MC carbides was found. The carbides in the 12Cr-lMo-V-W alloy were identified as chromium-rich M₂₃C₆ and vanadium-rich MC. The results give an indication of the sensitivity of these alloys to heat treatment variations. This paper is based on a presentation made at the “pcter G. Winchell Symposium on Tempering of Steel” held at the Louisville Meeting of The Metallurgical Society of AIME, October 12-13, 1981, under the sponsorship of the TMS-AIME Ferrous Metallurgy and Heat Treatment Committees.     

Precipitation Reactions during the Heat Treatment of Ferritic Steels

The precipitation reactions in two ferritic steels, 9Cr-1Mo-V-Nb and 12Cr-1Mo-V-W, were studied. Analytical electron microscopy, optical microscopy, electrolytic extractions, and hardness measurements were used to determine the types, amounts, and effects of precipitates formed as a function of the heat treatment. The effect of variations in the austenitizing treatment was ascertained. In addition to variations in the austenitizing time and temperature, different cooling rates after austenitization were also used. Air cooling after austenitization (normalization) resulted in little precipitation in both alloys. Precipitation in the 12Cr-1Mo-V-W alloy after furnace cooling was found in all cases examined. Under certain conditions precipitation was also found after furnace cooling the 9Cr-1Mo-V-Nb alloy. However, when compared to the amount of precipitate in the fully tempered state, the 9Cr-1Mo-V-Nb showed a much greater variation in the degree of precipitation following furnace cooling. In addition, the matrix microstructure of the 9Cr-1Mo-V-Nb alloy was very sensitive to cooling rate. The precipitation reactions during tempering after a normalizing treatment were followed as a function of tempering treatment. Tempering temperatures were varied from 400 to 780 °C. The carbide precipitation was essentially complete after one hour at 650 °C for both alloys. Analytical microscopy was used to identify the precipitates. In the 9Cr-1Mo-V-Nb alloy, a combination of chromium-rich M₂₃C₆ and vanadium-niobium-rich MC carbides was found. The carbides in the 12Cr-1Mo-V-W alloy were identified as chromium-rich M₂₃C₆ and vanadium-rich MC. The results give an indication of the sensitivity of these alloys to heat treatment variations. This paper is based on a presentation made at the “Peter G. Winchell Symposium on Tempering of Steel” held at the Louisville Meeting of The Metallurgical Society of AIME, October 12-13, 1981, under the sponsorship of the TMS-AIME Ferrous Metallurgy and Heat Treatment Committees.     

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.     

Carbides in high-speed steels containing silicon

The effects of silicon additions up to 3.5 wt pct on the as-cast carbides, as-quenched carbides, and as-tempered carbides of high-speed steels W3Mo2Cr4V, W6Mo5Cr4V2, and W9Mo3Cr4V were investigated. In order to further understand these effects, a Fe-16Mo-0.9C alloy was also studied. The results show that a critical content of silicon exists for the effects of silicon on the types and amount of eutectic carbides in the high-speed steels, which is about 3, 2, and 1 wt pct for W3Mo2Cr4V, W6Mo5Cr4V2, and W9Mo3Cr4V, respectively. When the silicon content exceeds the critical value, the M₂C eutectic carbide almost disappears in the tested high-speed steels. Silicon additions were found to raise the precipitate temperature of primary MC carbide in the melt of high-speed steels that contained d-ferrite, and hence increased the size of primary MC carbide. The precipitate temperature of primary MC carbide in the high-speed steels without d-ferrite, however, was almost not affected by the addition of silicon. It is found that silicon additions increase the amount of undis-solved M₆C carbide very obviously. The higher the tungsten content in the high-speed steels, the more apparent is the effect of silicon additions on the undissolved M₆C carbides. The amount of MC and M₂C temper precipitates is decreased in the W6Mo5Cr4V and W9Mo3Cr4V steels by the addition of silicon, but in the W3Mo2Cr4V steel, it rises to about 2.3 wt pct.     

Effects of heat treatment on wear resistance and fracture toughness of duo-cast materials composed of high-chromium white cast iron and low-chromium steel

The objective of this study is to investigate effects of heat treatment on wear resistance and fracture toughness in duo-cast materials composed of a high-chromium white cast iron and a low-chromium steel as a wear-resistant part and a ductile part, respectively. Different size, volume fraction, and distribution of M₇C₃ carbides were employed in the wear-resistant part by changing the amount of chromium, and the volume fraction of martensite in the austenitic matrix was varied by the heat treatment. In the alloys containing a small amount of chromium, an interdendritic structure of eutectic M₇C₃ carbides was formed, and led to the improvement of wear resistance and fracture toughness. After the heat treatment, the selective wear of the matrix and the cracking or spalled-off carbides were considerably reduced since the hardness difference between carbides and matrix decreased by the increase in the matrix hardness, thereby leading to the improvement of the wear resistance. However, the fracture toughness of the heat-treated alloys was lower than that of the as-cast alloys because the matrix containing a considerable amount of martensite did not effectively prevent the crack propagation.     

Effect of carbon concentration on precipitation behavior of M<Subscript>23</Subscript>C<Subscript>6</Subscript> carbides and MX carbonitrides in martensitic 9Cr steel during heat treatment

The distributions and precipitated amounts of M₂₃C₆ carbides and MX-type carbonitrides with decreasing carbon content from 0.16 to 0.002 mass pct in 9Cr-3W steel, which is used as a heat-resistant steel, has been investigated. The microstructures of the steels are observed to be martensite. Distributions of precipitates differ greatly among the steels depending on carbon concentration. In the steels containing carbon at levels above 0.05 pct, M₂₃C₆ carbides precipitate along boundaries and fine MX carbonitrides precipitate mainly in the matrix after tempering. In 0.002 pct C steel, there are no M₂₃C₆ carbide precipitates, and instead, fine MX with sizes of 2 to 20 nm precipitate densely along boundaries. In 0.02 pct C steel, a small amount of M₂₃C₆ carbides precipitate, but the sizes are quite large and the main precipitates along boundaries are MX, as with 0.002 pct C steel. A combination of the removal of any carbide whose size is much larger than that of MX-type nitrides, and the fine distributions of MX-type nitrides along boundaries, is significantly effective for the stabilization of a variety of boundaries in the martensitic 9Cr steel.     

Solidification of high-speed tool steels

Gradient solidification and differential thermal analysis (DTA) experiments were used to study the process of solidification and the solidification microstructure of 11 alloys comprising the composition range of customary commercial high-speed steels (with the exception of cobalt-alloyed grades). Also included are a number of experimental high-speed steels alloyed with niobium. The results include the effects of alloy composition and cooling rate on the width of the solidification interval and on the sequence of the solidification reactions; the types of eutectics formed (austenite with M₆C, M₂C, or MC) and their volume fractions; the chemical compositions of the ledeburitic and primary carbides; and the relation between the chemistry of the carbides and that of the melt. Special attention is given to the formation and composition of heterogeneously nucleated primary MC particles and to the chemistry and stability of eutectic M₂C, which is important as a precursor to MC and M₆C in the microstructure of finished (hot-worked and heat-treated) material.     

The postweld heat-treatment response of simulated coarse-grained heat-affected zones in a new ferritic steel

The tempering behavior of simulated coarse-grained (CG) heat-affected zones (HAZs) in two ferritic alloy steels, 2.25Cr-1Mo and HCM2S, was investigated. The hardness of HCM2S was found to be stable at longer times and higher temperatures than the 2.25Cr-1Mo steel, even though the “as-welded” hardnesses were approximately equal. Both materials reached a peak secondary hardness after tempering for 5 hours at 575 °C. The increase in hardness of the 2.25Cr-1Mo steel was due to precipitation of Fe-rich M₃C carbides within the prior-austenite grains, whereas the secondary hardening in HCM2S was due to a fine dispersion of intragranular, W-rich carbides. The HCM2S steel retained its hardness at longer times and higher temperatures than 2.25Cr-1Mo steel, because of the precipitation of intragranular, W-rich carbides and V-rich MC carbides that stabilized the lath structure. This study shows that HCM2S should not be heat treated in the same way as 2.25Cr-1Mo steel and also provides a basis for defining the postweld heat treatment (PWHT) of HCM2S.     

Effect of molybdenum on the kinetics of phase transformation of undercooled austenite in high-speed steels under continuous cooling

The aim of these investigations was to determine the effect of the ratio % Mo to % W in the austenite of high-speed steels on the kinetics of its transformation under continuous cooling. The investigations were carried out on model alloys. Three CCT curves were drawn. Also the influence of cooling velocity on the volume fraction of retained austenite in high-speed steels was evaluated. It was determined that with the increase of the Mo content in the high-speed steel matrix the M_S temperature decreases and the fraction of retained austenite increases, the development of the bainite transformation decreases and the stability of austenite increases in the range of diffusion transformations. With an increased cooling rate, the volume fraction of retained austenite decreases at first and then it increases. These changes are caused by the precipitation of carbides from undercooled austenite and can give rise to the differences in the content of retained austenite on the cross-section of quenched tools.     

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.     

The Transformation of Carbides during Austenization and Its Effect on the Wear Resistance of High Speed Steel Rolls

The transformation of carbides with austenization time of a high speed steel (HSS) roll material, manufactured by a centrifugal casting method, has been studied. The correlation between wear resistance and the type, morphology, volume fraction, and distribution of the carbides has also been investigated. Microstructural observations, X-ray diffraction (XRD) analysis, hardness measurements, and energy dispersive spectroscopy (EDS) have been used to characterize the carbides. The type and volume fraction of carbides were found to change with austenizing time. During austenization, the transformation of the M₃C carbides can be postulated as M₃C + γ-Fe → M₂C, with much finer nodular and rodlike MC carbides also forming through a solid-state transformation. The M₂C carbide decomposes as M₂C + γ-Fe → MC + M₇C₃ + M₆C. The decomposed carbide substantially maintains a platelike shape until the end of decomposition. The most important finding of this study is that austenization results in changes in the type, morphology, volume fraction, and distribution of carbides and that it can be controlled to produced a homogeneous distribution of hard carbides, resulting in an improvement in the wear resistance of HSS rolls. This finding may be of great use for the industrial production of HSS rolls.     

The microstructure of chromium-tungsten steels

Chromium-tungsten steels are being developed to replace the Cr-Mo steels for fusion-reactor applications. Eight experimental steels were produced and examined by optical and electron microscopy. Chromium concentrations of 2.25, 5, 9 and 12 pct were used. Steels with these chromium compositions and with 2 pct W and 0.25 pct V were produced. To determine the effect of tungsten and vanadium, three other 2.25Cr steels were produced as follows: an alloy with 2 pct W and 0 pct V and alloys with 0 and 1 pct W and 0.25 pct V. A 9Cr steel containing 2 pct W, 0.25 pct V, and 0.07 pct Ta also was studied. For all alloys, carbon was maintained at 0.1 pct. Two pct tungsten was required in the 2.25Cr steels to produce 100 pct bainite (no polygonal ferrite). The 5Cr and 9Cr steels were 100 pct martensite, but the 12Cr steel contained about 25 pct delta-ferrite. Precipitate morphology and precipitate types varied, depending on the chromium content. For the 2.25Cr steels, M₃C and M₇C₃ were the primary precipitates; for the 9Cr and 12Cr steels, M₂₃C₆ was the primary precipitate. The 5Cr steel contained M₇C₃ and M₂₃C₆. All of the steels with vanadium also contained MC.     

Effect of Cu Addition on Microstructure and Hardness of As-Cast and Heat-Treated High-Cr Cast Iron

The objective of the present study is to investigate the effect of Cu addition on microstructure and hardness of hypoeutectic high-Cr cast irons (26 wt% Cr) in as-cast and heat-treated conditions. As-cast specimens with varying amount of copper (Cu) addition were produced using an industrial grade high-frequency induction furnace. As-cast specimens were heat-treated in a box furnace using a typical reversed heat treatment sequence where subcritical heat treatment was followed by destabilization heat treatment. Microstructural analysis of the as-cast and heat-treated specimens was carried out using an optical microscope and Feritscope to understand the effect of Cu addition on the microstructure. The bulk hardness of all the specimens was measured using a Brinell hardness tester. The obtained result shows that the microstructures of the as-cast specimens mostly consist of austenitic dendrite matrix with γ+ M₇C₃ eutectic colony morphology. The eutectic colony consists of fine carbides in the central region and coarse carbides at the boundary region. High Cu containing specimen has a higher amount of thin rod-like M₇C₃ carbides, whereas low Cu containing specimen has a higher fraction of massive carbide morphology. Heat-treated specimens with various Cu content show mixed microstructure mostly consisting of retained austenite, transformed martensite, eutectic carbides, and secondary carbides. However, their relative volume fraction changes with the change in Cu content. Hardness result shows that higher Cu containing specimen has a lower hardness than the lower Cu contain specimens for both as-cast and heat-treated conditions. Although heat-treated specimens, in general, have higher hardness values than the as-cast specimens.     

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.