Tempering of 2.25 Pct Cr-1 Pct Mo Low Carbon Steels

The effect of carbon level on the tempering behavior at 700°C of 2.25 pct Cr-1 pct Mo steels having typical weld metal compositions has been investigated using analytical electron microscopy and X-ray diffraction techniques. The morphology, crystallography and chemistry, of each of the various types of carbides observed, has been established. It has been shown that each carbide type can be readily identified in terms of the relative heights of the EPMA spectra peaks for iron, chromium, molybdenum, and silicon. A decrease in the carbon level of the steel increases the rate at which the carbide precipitation reactions proceed, and also influences the final product. Of the carbides detected, M₂₃C₆ and M₇C₃ were found to be chromium-based, and their compositions were independent of both the carbon level of the steel and the tempering time. The molybdenum-based carbides, M₂C and M₆C, however, showed an increase in their molybdenum contents as the tempering time was increased. The rate of this increase became greater as the carbon content of the steel was lowered.     

Effect of long-term service exposure at elevated temperature on microstructural changes of 5Cr-0.5Mo steels

Effects of long-term service exposure at elevated temperature on microstructural changes have been studied for both virgin and service-exposed process heater tube pipes of 5Cr-0.5Mo steels used in oil refineries. Samples selected for this study had experienced a nominal temperature range of 450 °C to 500 °C for about 20 to 25 years. Two different initial virgin microstructures were taken and designated by steel A and steel B. The virgin microstructure of steel A exhibited fine platelets of fibrous or hairlike M₂C carbides within the ferrite grains and occasionally irregularly shaped M₂₃C₆, both along the grain boundaries and at the grain interiors, and very few spheroidally shaped M₃C, either along the grain boundaries or at the grain interiors. The size, shape, position, distribution, and type of carbides in virgin steel A changed significantly due to 220,000 hours of service exposure in the temperature range of 450 °C to 500 °C. Massive M₂₃C₆ carbides precipitated along the grain boundaries. In addition, regular geometrically shaped M₂₃C₆ carbides, such as hexagonal, square, and triangular type, were observed to form at the grain interiors. The virgin steel B microstructure exhibited predominantly M₂₃C₆ carbides, either along the grain boundaries or at the lath boundaries. Occasionally, fine platelets of M₂C carbides were also observed within the laths. The position, shape, distribution, and type of carbides did not change significantly due to 172,000 hours of service exposure in the temperature range of 450 °C to 500 °C. The average interparticle spacings of the carbides increased from 0.35 to 1.2 μm due to 172,000 hours of exposure.     

Identification of M5C2 carbides in ex- service 1Cr-0.5Mo steels

Rod-shaped precipitates up to 6μm} long and 0.25μm wide, observed as a common feature within proeutectoid ferrite grains of ex-service lCr-0.5Mo steels, have been characterized using electron microdiffraction, energy-dispersive X-ray spectroscopy, and electron energy loss spectroscopy. The majority of the rods have been identified as M₅C₂ carbides, although some were M₃C. The M₅C₂ carbide, also known as the Hägg orX-carbide, is a monoclinic phase that is not known to have been identified previously in creep-resistant Cr-Mo steels. The M₅C₂ rods appeared to nucleate heterogeneously on M₂C carbides and persist in ferrite regions from which the needlelike M₂C carbides had disappeared. This suggests that the M₅C₂ carbide is more stable thermodynamically than M₂C in lCr-0.5Mo steels under typical service conditions. The metallic element compositions of the rodlike carbides varied, but the average compositions were in the range 48 to 56 at. pct Fe, 32 to 42 at. pet Cr, 8 to 12 at. pct Mn, and about 1 at. pct Mo. The Mn content of the rods varied systematically with exposure temperature and thus might be applied to the estimation of the effective service temperature of lCr-0.5Mo steel components.     

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.     

Carbon Redistribution and Carbide Precipitation in a High-Strength Low-Carbon HSLA-115 Steel Studied on a Nanoscale by Atom Probe Tomography

HSLA-115 is a newly developed Cu-bearing high-strength low-carbon martensitic steel for use in Naval structural applications. This research provides, for the first time, a comprehensive compositional analysis of carbon redistribution and associated complex phase transformations in an isothermal aging study of HSLA-115 at 823 K (550 °C). Specifically, we characterize carbon segregation at lath boundaries, grain-refining niobium carbonitrides, cementite, and secondary hardening M₂C carbides, in addition to copper precipitation, by 3D atom probe tomography (APT). Segregation of carbon (3 to 6 at. pct C) is observed at martensitic lath boundaries in the as-quenched and 0.12-hour aged microstructures. On further aging, carbon redistributes itself forming cementite and M₂C carbides. Niobium carbonitride precipitates do not dissolve during the austenitizing treatment and are inherited in the as-quenched and aged microstructures; these are characterized along with cementite by synchrotron X-ray diffraction and APT. Sub-nanometer-sized M₂C carbide precipitates are observed after the formation of Cu precipitates, co-located with the latter, indicating heterogeneous nucleation of M₂C. The temporal evolution of the composition and morphology of M₂C carbides at 823 K (550 °C) is described using APT; their precipitation kinetics is intertwined with Cu precipitates, affecting the bulk mechanical properties of HSLA-115. Phase compositions determined by APT are compared with computed compositions at thermodynamic equilibrium using ThermoCalc.     

Studies of Carbides in a Rapidly Solidified High-Speed Steel

Rapid solidification by electron beam surface melting of a Mo-base high-speed steel (M7) has produced microstructural features different from those observed in the conventionally processed material. As a result of rapid solidification, the volume percent of the carbide phases formed has decreased sharply and has resulted in the formation of M₂C and M₂₃C₆ carbide phases, while in the conventionally processed material, M₆C and MC carbides were present. Microanalysis of the extracted carbides formed by electron beam melting has yielded an intriguing finding. M₂₃C₆ is found to be unusually rich in molybdenum, tungsten, and vanadium; the concentration of (Mo + W), for instance, is approximately 60 wt pct. The corresponding values for Fe and Cr are surprisingly low (6 wt pct Cr and 1 wt pct Fe). This is in marked contrast with carbides encountered in the conventionally processed high-speed steel, where Cr and Fe are the major constituents. The shift in composition of the carbide phases could be attributed to the accelerated evaporation of chromium during surface melting as compared to the evaporation of Mo, W, and V. formerly Research Associate, University of Connecticut     

Embrittlement of 21/4 CrMoV steel bolts after long exposure at 540 °C

Bolts made of2 ^1/4 CrMoV steel became gradually embrittled and exhibited an increasing fraction of intercrystalline fracture after long exposure (more than 25,000 h) at 540 °C. This has been found to be caused by the segregation of phosphorus to the prior austenite grain boundaries. This was accompanied by the depletion of molybdenum in the ferrite down to about 0.3 pct owing to the formation of a molybdenum-containing carbide Fe₃Mo₃C(M₆C). Reheating of the embrittled bolts to 680 °C removed the segregation of phosphorus at the grain boundaries and therefore also removed the intercrystalline embrittlement. However, the molybdenum content of the ferrite was lowered further to about 0.2 pct; hence the scavenging of phosphorus by molybdenum was further reduced, and therefore the embrittling tendency of these bolts during reuse was increased. Even after reaustenitizing, quenching and tempering, the service life of these bolts was found to be shorter than in the original condition; this is presumed to be due to an inhomogeneity of molybdenum in the austenite not removed by the reaustenitizing treatment.     

Correlation of microstructure with the wear resistance and fracture toughness of duocast materials composed of high-chromium white cast iron and low-chromium steel

The objective of this study is to investigate the correlation of microstructure with wear resistance and fracture toughness in duocast materials that consisted of a high-chromium white cast iron and a low-chromium steel as the wear-resistant and ductile parts, respectively. Different shapes, sizes, volume fractions, and distributions of M₇C₃ carbides were employed in the wear-resistant part by changing the amount of chromium and molybdenum. In the alloys containing a large amount of chromium, a number of large hexagonal-shaped primary carbides and fine eutectic carbides were formed. These large primary carbides were so hard and brittle that they easily fractured or fell off from the matrix, thereby deteriorating the wear resistance and fracture toughness. In the alloys containing a smaller amount of chromium, however, a network structure of eutectic carbides having a lower hardness than the primary carbides was developed well along solidification cell boundaries and led to the improvement of both wear resistance and toughness. The addition of molybdenum also helped enhance the wear resistance by forming additional M₂C carbides without losing the fracture toughness. Under the duocasting conditions used in the present study, the appropriate compositions for wear resistance and fracture toughness were 17 to 18 pct chromium and 2 to 3 pct molybdenum.     

Modeling M6C precipitation in niobium-alloyed ferritic stainless steel

Niobium is used as an important alloying element in the design of heat-resistant stainless steels for automotive exhaust systems. When in solid solution, the niobium improves both the high-temperature strength and the resistance to thermal fatigue life. However, it also forms coarse Fe₃Nb₃C carbides during service at elevated temperatures, making it important to understand the kinetics of carbide precipitation and coarsening. In the present work, the kinetics of M₆C precipitation in ferrite have been modeled, taking into account the multicomponent nature of the diffusion process while at the same time allowing for capillarity effects. The lack of appropriate thermodynamic data has been dealt with using a solubility product based on new experiments on a 19Cr-0.8Nb mass pct steel.     

Effects of alloying additions and austenitizing treatments on secondary hardening and fracture behavior for martensitic steels containing both Mo and W

The effects of alloying additions and austenitizing treatments on secondary hardening and fracture behavior of martensitic steels containing both Mo and W were investigated. The secondary hardening response and properties of these steels are dependent on the composition and distribution of the carbides formed during aging (tempering) of the martensite, as modified by alloying additions and austenitizing treatments. The precipitates responsible for secondary hardening are M₂C carbides formed during the dissolution of the cementite (M₃C). The Mo-W steel showed moderately strong secondary hardening and delayed overaging due to the combined effects of Mo and W. The addition of Cr removed secondary hardening by the stabilization of cementite, which inhibited the formation of M₂C carbides. The elements Co and Ni, particularly in combination, strongly increased secondary hardening. Additions of Ni promoted the dissolution of cementite and provided carbon for the formation of M₂C carbide, while Co increased the nucleation rate of M₂C carbide. Fracture behavior is interpreted in terms of the presence of impurities and coarse cementite at the grain boundaries and the variation in matrix strength associated with the formation of M₂C carbides. For the Mo-W-Cr-Co-Ni steel, the double-austenitizing at the relatively low temperatures of 899 to 816 °C accelerated the aging kinetics because the ratio of Cr/(Mo + W) increased in the matrix due to the presence of undissolved carbides containing considerably larger concentrations of (Mo + W). The undissolved carbides reduced the impact toughness for aging temperatures up to 510 °C, prior to the large decrease in hardness that occurred on aging at higher temperatures.     

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.     

Effect of long-term service exposure on microstructure and mechanical properties of a crmov steam turbine rotor steel

The influence of prolonged service exposure on the microstructure and mechanical properties of a 1Cr-1Mo-0.25V steam turbine rotor steel has been studied. The samples for this study were taken from four locations of a rotor which had operated for 23 years. The operating temperatures at these locations were 288 °C, 425 °C, 510 °C, and 527 °C. The impact of retempering at 677 °C of steel exposed at 425 °C was also investigated. Service exposure at 288 °C brought no noticeable changes in either tensile properties or microstructure; the steel contained coarse bainitic cementite, extremely fine spheroidal MC, and thin platelets of M₂C. Service exposure at 510 °C led to profuse precipitation of cementite along grain boundaries in addition to increasing M₂C precipitation. These changes resulted in a slight decrease in the yield and tensile strengths and a marginal increase in ductility. Service exposure at 527 °C produced grain boundary precipitation of M₂₃C6, coarsening of MC, and more profuse precipitation of M₂C and caused a considerable decrease in strength and an increase in ductility. Retempering at 677 °C for 24 hours resulted in more precipitation of M₂₃C₆ and considerable coarsening of MC, without affecting further the size or shape of M₂C. The strength of the steel decreased drastically and the reduction in area increased considerably due to retempering. These changes in microstructure and mechanical properties indicate that service exposure at 527 °C for 23 years did not produce a stable microstructure. The microstructure and mechanical properties of the rotor steel would continue to deteriorate in future operation.     

Effect of structural factors on the creep properties of modified chromium steels

The precipitation strengthening of modified chromium steels is effected predominantly by M₂₃C₆ carbides. In molybdenum-modified 9% chromium steels, creep resistance depends on the dispersion of the M₂₃C₆ carbides and on the molybdenum content in the solid solution. There is no point in increasing molybdenum contents of molybdenum-modified steels above approximately 1 wt.%. In vanadium-modified steels precipitation strengthening is effected both by M₂₃C₆ carbides and by VC_xN_y carbonitrides. If the amount of nitrogen in solid solution is insufficient, this reduces the volume fraction of VC_xN_y in the structure and thus impairs the creep resistance of the steel. It is advisable to restrict the aluminium and titanium contents in the vanadium-modified chromium steels.     

Solidification microstructure and M2C carbide decomposition in a spray-formed high-speed steel

The solidified carbide morphology, the decomposition behavior of the M₂C carbide, and the carbide distribution after forging of an Fe-1.28C-6.4W-5.0Mo-3.1V-4.1Cr-7.9Co (wt pct) high-speed steel prepared by spray forming have been investigated. The spray-formed microstructure has been characterized as a discontinuous network of plate-shaped M₂C carbides and a uniform distribution of fine, spherical MC carbides. The metastable M₂C carbides formed during solidification have been fully decomposed into MC and M₆C carbides after sufficient annealing at high temperatures. Initially, the M₆C carbides nucleate at M₂C/austenite interfaces and proceed to grow. In the second stage, the MC carbides form either inside the M₆C carbides or at the interfaces between M₆C carbides. With this increasing degree of decomposition of the M₂C carbide, the carbides become more uniformly distributed through hot forging, which produces a significant increase in ultimate bend strength. The decomposition treatment of M₂C carbide has been found to be most important for obtaining a fine homogeneous carbide distribution after hot forging.     

Structures and tempering behavior of rapidly solidified high-carbon iron alloys

High-carbon iron alloys containing carbide formers of chromium and molybdenum were rapidly solidified by means of a single roller method. In the alloy containing a high level of both chromium and molybdenum (10Cr-5Mo) and a critical carbon content of about 4 pct, the metastable phases,ε phase and austenite, are retained after solidification. Theε phase could contain a large amount of carbon in solid solution so that during tempering at about 900 K, it decomposes to very fine ferrite and carbide, which bring about an enhanced hardness of 1300 DPN. Even after tempering at a high temperature around 1100 K, the hardness hardly deteriorates due to a remarkable dispersion of fine M₃C and M₇C₃ carbides. Thus, coaddition of chromium and molybdenum is effective in obtaining high hardness. Formerly Graduate Student, Kyushu Institute of Technology     

Crystallography and Morphology of Carbides in a Low-Cycle Fatigued 1Cr-1Mo-0.25V Steel

The carbide precipitation in 1Cr-1Mo-0.25V steel subjected to low-cycle fatigue (LCF) deformation at room and elevated temperatures was investigated by means of transmission electron microscopy. Based on the electron diffraction analyses, three types of carbides, M₃C-type cementite, M₂C, and MC, were identified in normalized and subsequently tempered specimen. The cyclic deformation at high temperature led to the following changes in morphology and composition of carbides: the spheroidization of cementite, the enhanced precipitation of H-carbide, the formation of M₂C and M₂₃C₆ at lath or prior-austenite grain boundaries, and the enrichment of Mo in most of carbides. Particular attention has been paid to the crystallographic orientation relationship (OR) between the cementite and the ferrite (α) matrix. The combined analyses based on the simulation of diffraction patterns and the trace analyses of habit plane on stereographic projection have shown that most cementite was related to the α matrix in accordance with Bagaryatskii OR, but in some cases, the Isaichev OR also was observed in the lath interior after LCF deformation at elevated temperature. In addition, M₂C obeyed the Burgers–Jack OR, and MC was related to the α by the Baker–Nutting OR.     

Effects of tungsten content on the creep-rupture properties of low-carbon cobalt-base heat-resistant alloys

The effects of tungsten (W) content up to about 20 wt pct on the creep-rupture properties of low-carbon HAYNES 25-(L-605-) type cobalt-base alloys were investigated at 1089 and 1311 K. An increase in W content of about 5 wt pct resulted in tripling the rupture life without significant loss of creep ductility at 1311 K. The principal strengthening phases precipitated during creep at 1311 K were W solid solution and M₆C carbide precipitates in the matrix and on the grain boundaries. The amounts of these precipitates, especially precipitates of W solid solution, increased with increasing W content. The Cr₂₃C₆ carbide was also detected in those ruptured specimens of alloys containing more than 17 wt pct W. The creep ductility decreased a little, and the rupture life did not increase with increasing W content at 1089 K. Two types of carbides (Cr₂₃C₆ and M₆C), Co₂W (Laves phase), and α-Co were confirmed in the specimens ruptured at 1089 K. The amount of Co₂W harmful to ductility, as well as the amounts of strengthening phases (carbides), increased with increasing W content.     

Identification of Inverse Bainite in Fe-0.84C-1Cr-1Mn Hypereutectoid Low Alloy Steel

A unique dilatation trend is observed for isothermal bainite transformation in Fe-0.84 pct C-1 pct Cr-1 pct Mn steel. The dilatation is found to occur in two stages with volumetric contraction dominating the first stage, followed by volumetric expansion dominating the second stage. Through electron microscopic characterization, bainitic microstructure is identified as inverse bainite with cementite (Fe₃C) nucleating first from supersaturated austenite followed by the transformation of ferrite and secondary carbides (Fe₃C, Fe₂C, and Fe₅C₂) from carbon-depleted austenite.     

The crystallography of secondary carbide precipitation in high speed steel

Precipitation of secondary carbides in a powder metallurgical high speed steel, ASP 23, has been investigated by transmission electron microscopy. Particular attention has been paid to the crystallographic orientation relationships between the precipitated phases and the ferrite matrix. During the hardening treatment prior to tempering, cementite precipitates on prior-austenite grain boundaries and twin boundaries within the martensite plates. The cementite is oriented with respect to one of the adjacent ferrite lattices according to the Bagaryatskii orientation relationship. During tempering at 560°C the cementite coarsens and fine dispersions of MC and M₂C precipitate within the martensite plates. MC obeys the Baker-Nutting orientation relationship while M₂C obeys both the Pitsch-Schrader orientation relationship and another relationship defined by: (0001)_M2C//(021)_x; (11¯20)_M2C//(100)_x; (¯1100)_M2C//(01¯2)_x. The coexistence of both of these orientation relationships for M₂C precipitated in ferrite is explained in terms of the near-coincident site lattice model.     

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}.