Interstitial atom configurations in stable and metastable Fe-N and Fe-C solid solutions

Mössbauer Fe⁵⁷ spectroscopy allows comparison of Fe?N and Fe?C interstitial solid solutions. The spectra of Fe?N retained austenite indicate that nitrogen atoms are randomly distributed on octahedral sites in the austenite and in the virgin martensite. On heating, austenite decomposes directly to the equilibrium phases α iron and Fe₄N at temperatures above 160°C. Virgin martensite ages at room temperature by local ordering of nitrogen atoms. In that process, three new iron atom environments develop, characteristic of the Fe₁₆N₂ (α″) structure. However, the excessive width of the peaks indicate the perfect order of the Fe₁₆N₂ precipitate is not achieved, except after very long times. Further aging at 100°C leads to the complete decomposition of the virgin martensite to the discrete phases α iron and Fe₁₆N₂. This two phase structure is stable up to 160°C, above which the precipitation of Fe₄N occurs. These results are in contrast to Fe?C data. Carbon atoms in retained austenite tend to be far apart in their octahedral sites, and this nonrandom distribution is inherited by the virgin martensite. Fe?C austenite decomposes by the formation of ∈ carbide below 160°C and precipitation of Fe₃C above 180°C. The carbon atoms in virgin martensite agglomerate at room temperature and regions of ordered Fe₄C are believed to result. Subsequently ∈ carbon is formed at 80°C and Fe₃C precipitates above 160°C.¹     

Retained Austenite and Tempered Martensite Embrittlement in Medium Carbon Steels

Electron microscopy, diffraction and microanalysis, X-ray diffraction, and auger spectroscopy have been used to study quenched and quenched and tempered 0.3 pct carbon low alloy steels. Some in situ fracture studies were also carried out in a high voltage electron microscope. Tempered martensite embrittlement (TME) is shown to arise primarily as a microstructural constraint associated with decomposition of interlath retained austenite into M₃C films upon tempering in the range of 250 °C to 400 °C. In addition, intralath Widmanstätten Fe₃C forms from epsilon carbide. The fracture is transgranular with respect to prior austenite. The situation is analogous to that in upper bainite. This TME failure is different from temper embrittlement (TE) which occurs at higher tempering temperatures (approximately 500 °C), and is not a microstructural effect but rather due to impurity segregation (principally sulfur in the present work) to prior austenite grain boundaries leading to intergranular fracture along those boundaries. Both failures can occur in the same steels, depending on the tempering conditions.     

Austenite ferromagnetism and martensite morphology

The Curie temperature of the austenite, the martensite-start temperature, and martensite morphology have been determined in a series of nil-carbon Fe?Ni and Fe?Ni?Co alloys. For these alloys, austenite ferromagnetism aboveM _s is a necessary, but not sufficient, condition for the formation of lenticular rather than packet martensite. In contrast to Fe?Ni alloys where lenticular martensite only forms below ≈O°C, some of the Fe?Ni?Co alloys transform to this structure at temperatures up to ≈200°C. The results support the hypothesis that the resistance of austenite to plastic deformation affects the habit plane and thus morphology of the martensite which forms.     

Optimization of Fe/Cr/C base structural Steels for improved strength and toughness

Optimization of the composition and the heat treatments to provide a microduplex structure of dislocated-autotempered lath martensite and thin film retained austenite for good combinations of mechanical properties has been attained for Fe/Cr/C base steels. Substituting 0.5 wt pct Mo to reduce Cr from 4 pct to 3 pct did not affect the microstructures nor the properties. It was found that air melting as compared to vacuum melting does not cause deterioration of toughness in Mn containing alloys but does so in Ni containing alloys. Tempered martensite embrittlement was confirmed as being due to the decomposition of retained austenite. Further improvements in the fracture toughness are achieved by double heat treatments which provide grain refinement. These alloys are considered to be very promising for structural applications.     

A study of the early stages of tempering in an Fe-1.2 Pct alloy

Mössbauer effect spectroscopy has been used to study changes in the microstructure of an Fe-1.22. wt pct C alloy due to tempering between 373 and 523 K. The orthorhombic transition carbide, η-Fe₂C, was identified by transmission electron microscopy and the similarity of ∈-carbide electron diffraction patterns to η-carbide diffraction patterns is noted. Systematic changes in the Mosbauer parameters of martensite and austenite are presented for the various stages of tempering. The same amount of C remains randomly dissolved in the retained austenite throughout tempering and some C is retained in the martensite throughout the range of transition carbide formation. Two sets of Mössbauer parameters corresponding to magnetic phases other than martensite and cementite have been found. These parameters may come from η-carbide, but alternative interpretations are presented.     

Retained Austenite Decomposition and Carbide Formation During Tempering a Hot-Work Tool Steel X38CrMoV5-1 Studied by Dilatometry and Atom Probe Tomography

The microstructural development of a hot-work tool steel X38CrMoV5-1 during continuous heating to tempering temperature has been investigated with the focus on the decomposition of retained austenite (Stage II) and carbide formation (Stages III and IV). Investigations have been carried out after heating to 673.15?K, 773.15?K, 883.15?K (400?°C, 500?°C, 610?°C) and after a dwell time of 600?seconds at 883.15?K (610?°C). Dilatometry and atom probe tomography were used to identify tempering reactions. A distinctive reaction takes place between 723.15?K and 823.15?K (450?°C and 550?°C) which is determined to be the formation of M₃C from transition carbides. Stage II could be evidenced with the atom probe results and indirectly with dilatometry, indicating the formation of new martensite during cooling. Retained austenite decomposition starts with the precipitation of alloy carbides formed from nanometric interlath retained austenite films which are laminary arranged and cause a reduction of the carbon content within the retained austenite. Preceding enrichment of substitutes at the matrix/carbide interface in the early stages of Cr₇C₃ alloy carbide formation could be visualised on the basis of coarse M₃C carbides within the matrix. Atom probe tomography has been found to be very useful to complement dilatational experiments in order to characterise and identify microstructural changes.     

Mechanisms of tempered martensite embrittlement in low alloy steels

An investigation into the mechanisms of tempered martensite embrittlement (TME), also know as “500°F” or “350°C” or one-step temper embrittlement, has been made in commercial, ultra-high strength 4340 and Si-modified 4340 (300-M) alloy steels, with particular focus given to the role of interlath films of retained austenite. Studies were performed on the variation of i) strength and toughness, and ii) the morphology, volume fraction and thermal and mechanical stability of retained austenite, as a function of tempering temperature, following oil-quenching, isothermal holding, and continuous air cooling from the austenitizing temperature. TME was observed as a decrease in bothK _Ic and Charpy V-notch impact energy after tempering around 300°C in 4340 and 425°C in 300-M, where the mechanisms of fracture were either interlath cleavage or largely transgranular cleavage. The embrittlement was found to be concurrent with the interlath precipitation of cementite during temperingand the consequent mechanical instability of interlath films of retained austenite during subsequent loading. The role of silicon in 300-M was seen to retard these processes and hence retard TME to higher tempering temperatures than for 4340. The magnitude of the embrittlement was found to be significantly greater in microstructures containing increasing volume fractions of retained austenite. Specifically, in 300-M the decrease inK _Ic, due to TME, was a 5 MPa√m in oil quenched structures with less than 4 pct austenite, compared to a massive decrease of 70 MPa√m in slowly (air) cooled structures containing 25 pct austenite. A complete mechanism of tempered martensite embrittlement is proposed involving i) precipitation of interlath cementite due to partial thermal decomposition of interlath films of retained austenite, and ii) subsequent deformation-induced transformation on loading of remaining interlath austenite, destabilized by carbon depletion from carbide precipitation. The deterioration in toughness, associated with TME, is therefore ascribed to the embrittling effect of i) interlath cementite precipitates and ii) an interlath layer of mechanically-transformed austenite,i.e., untempered martensite. The presence of residual impurity elements in prior austenite grain boundaries, having segregated there during austenitization, may accentuate this process by providing an alternative weak path for fracture. The relative importance of these effects is discussed. Formerly with the Lawrence Berkeley Laboratory, University of California.     

Effects of coherent interfaces in the freshly formed ironnickelcarbon martensites

Evidence for a coherent bond at the interfaces between retained austenite and as-quenched martensite in FeNiC alloys and the relation of coherent interfaces to the abnormally high tetragonality of martensite are presented. The iron based alloys with 20 Ni-0.73 C, 28 Ni-0.2 C, 20 Ni-1.2 C, 25 Ni-0.7 C, 30 Ni-0.37 C, 33.5 Ni-0.01 C (in wt%) were studied by means of X-ray and neutron diffraction, Mössbauer spectroscopy, internal friction, electrical resistivity and magnetic susceptibility. It is shown that the break of coherency occurs during heating of the freshly formed twinned martensite in the temperature range of 100–200 K and it is accompanied by a relaxation of stresses in the retained austenite and a decrease of tetragonality. A new internal friction peak centered at 145 K was observed and attributed to movement of coherent interfaces and to the subsequent break of coherency. The relation between abnormally high tetragonality and coherency at the interface was confirmed in experiments with external deformation of virgin martensite at temperatures around 100 K. It is shown that the plate morphology of martensite is a necessary condition for a coherent bond at the interface. A possible role of atomic ordering of austenite in abnormally high tetragonality is discussed. Mössbauer measurements gave evidence for nickel-rich regions in initial austenite. During quenching the regions with the highest nickel content were assumed to remain austenitic inside the martensite plates. The conclusion about the coherency at the interface between the freshly formed martensite and the ordered regions in the retained austenite and at the interface along the martensite plates as a reason for high tetragonality of the FeNiC martensite with plate morphology is made.     

Stabilization of retained austenite due to partial martensitic transformations

The stabilization effect of retained austenite has been studied using FeNiC alloys with M_s temperatures below 0°C via a two-step cooling procedure, i.e. the samples were first cooled to a temperature (T_a) below M_s temperature and then heated to room temperature (RT), after being held at RT for a while, the samples were recooled to low temperatures (23 or 82 K) and then heated to RT. It was found that, during the second step of cooling, the martensitic transformation occurred at a temperature of M_s′ which was lower than T_a. With increasing the amount of martensite formed during the first cooling, the difference in the martensitic transformation starting temperatures, ΔM_s = M_s − M_s′, increased. The mechanism of the stabilization of retained austenite during the second step of cooling is proposed to be mainly due to the inhibition effect produced by the previously formed martensite. The aging processes, which retard the growth of the previously formed martensite plates and reduce the number of the available nucleation sites, are the necessary conditions for the above mechanism to operate. By simplifying the internal resisting stress acting on the retained austenite due to the existence of martensite phase as a hydrostatic compressive stress, which increases with increasing the amount of martensite, the change in ΔM_s is discussed from a thermodynamic point of view.     

Magnetic investigation of martensite ⇌ austenite transformations in Fe-Ni-Co alloys

The martensite ⇌ austenite transformations were investigated in Fe-Ni-Co alloys containing about 65 wt pct Fe and up to 15 wt pct Co. A change in morphology of martensite from plate-like to lath-type occurred with increasing cobalt content; this change in morphology correlates with the disappearance of the Invar anomaly in the austenite. The martensite-to-austenite reverse transformation differed depending on martensite morphology. Reversion of plate-like martensite was found to occur by simple disintegration of the martensite platelets. Reverse austenite formed from lath-type martensite was not retained when quenched from much aboveA _s, with microcracks forming during theM→γ→M transformation.     

The effect of austenitizing temperature on the microstructure and mechanical properties of as-quenched 4340 steel

The effect of austenitizing temperature on both the plane strain fracture toughness,K _IC , and the microstructure of AISI 4340 was studied. Austenitizing temperatures of 870 and 1200°C were employed. All specimens austenitized at 1200°C were furnace cooled from the higher austenitizing temperature and then oil quenched from 870°C. Transmission electron microscopy revealed an apparent large increase in the amount of retained austen-ite present in the specimens austenitized at the higher temperature. Austenitizing at 870°C resulted in virtually no retained austenite; only minor amounts were found sparsely scat-tered in those areas examined. A considerably altered microstructure was observed in specimens austenitized at 1200°C. Fairly continuous 100 to 200Å thick films of retained austenite were observed between the martensite laths throughout most of the area exam-ined. Additionally, specimens austenitized at 870°C contained twinned martensite plates while those austenitized at 1200°C showed no twinning. Plane strain fracture toughness measurements exhibited an approximate 80 pct increase in toughness for specimens austen-itized at 1200°C compared to those austenitized at 870°C. The yield strength was unaffected by austenitizing temperature. The possible role of retained austenite and the elimination of twinned martensite in the enhancement of the fracture toughness of those specimens austen-itized at the higher temperature will be discussed.     

Phase transformations during tempering of the Fe-15Cr-1Mo martensites containing nitrogen or carbon

Hardness measurements, dilatometry, internal friction measurements, Mössbauer spectroscopy and transmission electron microscopy are utilized in order to study the effect of tempering on the microstructure of a stainless martensitic steel containing 15% Cr, 1% Mo and 0.6% N. A similar carbon steel containing 15% Cr, 1% Mo and 0.6% C is used for comparison. Tempering of alloy Fe-15Cr-1Mo-0.6N in the low temperature range of 353-473 K leads to formation of hexagonal ?-nitride (Fe,Cr)₂N, which is followed by precipitation of the orthorombic ?-nitride (Fe,Cr)₂N at temperatures of 573-773 K. The hexagonal nitride Cr₂N is precipitated at 923 K and preferably formed at grain boundaries. The alloy Fe-15Cr-1Mo-0.6C shows the expected tempering behaviour. ?-carbide (Fe,Cr)₂C and cementite (Fe,Cr)₃C are precipitated during low temperature ageing, followed by the formation of Cr₇C₃ carbides after the temperature has risen to 873 K. With a similar interstitial content the amount of retained austenite in the nitrogen martensite is nearly twice as high as in the carbon one. Furthermore, the thermal stability of the retained austenite of the nitrogen alloy is substantially higher than that of the carbon steel.     

Isothermal martensite formation in an AISI 52100 ball bearing steel

The formation of isothermal martensite from the retained austenite in an AISI 52100 ball bearing steel was investigated. Optical microscopy reveals that there are mainly two types of isothermal martensite formation: the growth of the athermal martensite and the nucleation and growth of new martensite in the retained austenite. X-ray diffraction shows that during the isothermal transformation, the ratio of lattice constantsc/a decreases, and TEM verifies the precipitation of Fe, Cr)₃C in martensite. The kinetics of the isothermal transformation in the quenched steel also shows “C” shape characteristic. At the first stage of the isothermal formation, recovery of the athermal martensite occurs with an activation energy of 91.8 kJ mol^-1, implying that the diffusion of carbon in athermal martensite results in the precipitation of carbide and the relaxation of the strain energy at the martensite/matrix boundary. In the second stage, the activation energy for the isothermal formation is 130 kJ mol^-1; that may be the energy required for the rearrangement of the configuration of dislocations, forming preferred sites for nucleation. Formerly Graduate Student. Formerly Graduate Student, Department of Materials Science and Engineering.     

Forming response of retained austenite in a C‐Si‐Mn high strength TRIP sheet steel

TRIP sheet steels typically consist of ferrite, bainite, retained austenite, and martensite. The retained austenite is of particular importance because its deformation‐induced transformation to martensite contributes to excellent combinations of strength and ductility. While information is available regarding austenite response in uniaxial tension, less information is available for TRIP steels with respect to the forming response of retained austenite in complex strain states. Therefore, the purpose of this work was to study the austenite transformation behaviour in different strain paths by determining the amount of retained austenite before and after forming. Forming experiments were performed on a high strength 0.19C‐1.63Si‐1.59Mn TRIP sheet steel 1.2 mm in thickness in two different strain conditions, uniaxial tension (ε₁ = ‐2ε₂) and balanced biaxial stretching (ε₁ = ε₂). Specimens were formed to strains ranging from zero to approximately 0.2 effective (von Mises) strain. Specimens were tested both longitudinally and transverse to the rolling direction in uniaxial tension, and subtle mechanical property differences were found. The volume fraction of austenite, determined with X‐ray diffraction subsequent to forming, was found to decrease with increasing strain for both forming modes. Some modification in the crystallographic texture of the ferrite was observed with increasing strain, in specimens tested in the balanced biaxial stretch condition. This trend was not evident in the uniaxial tensile test results. Slight differences were found in the transformation behaviour of the austenite when formed in different strain conditions. More austenite transformed in specimens tested parallel to the rolling direction than transverse to the rolling direction in uniaxial tension. The amount of austenite transformed during biaxial stretching was determined to be greater than the amount transformed in uniaxial tension for specimens tested transverse to the rolling direction at an equivalent von Mises strain. The amount of austenite that transformed in biaxial tension, however, was comparable to the amount of austenite that transformed in specimens tested longitudinal to the rolling direction in uniaxial tension.     

Effect of Cryogenic Treatment on Property of 14Cr2Mn2V High Chromium Cast Iron Subjected to Subcritical Treatment

Effect of cryogenic treatment on the microstructure, hardening behavior and abrasion resistance of 14Cr2Mn2V high chromium cast iron （HCCI） subjected to subcritical treatment was investigated. The results show that cryogenic treatment after subcritical treatment can obviously improve the hardness and abrasion resistance of HCCI because abundant retained austenite is transformed into martensite and fine secondary carbides E（Fe, Cr）23 C6 ] precipitate. The amount of martensite and precipitated secondary carbide in HCCI experiencing subcritical treatment followed by cryogenic treatment was more than that experiencing the subcritical treatment followed by air cooling. When the abrasion resistance of HCCI reaches the maximum, its microstructure contains about 15 % retained austenite. Cryogenic treatment can further reduce the austenite content but the retained austenite cannot be transformed in to martensite completely.     

铁镍合金马氏体逆相变的织构研究

研究了在不同组织状态冷轧的Ｆｅ－３０Ｎｉ合金从马氏体到奥氏体逆相变过程中的织构变化。原始材料的组织状态为形变马氏体、淬火马氏体及残余奥氏体。经过在不同温度加热后，利用Ｘ射线衍射精确测量了马氏体及奥氏体的完全极图。结果表明，在不同组织状态下冷轧的Ｆｅ－３０Ｎｉ合金，经过γ－α－γｒ相变循环后，原冷轧奥氏体织构均得以恢复，逆相变奥氏体的取向分布只与原冷轧奥氏体的取向分布有关，与马氏体取向分布无关     

Plastic deformation of quenched and tempered 52100 bearing steel in compression

The compressive flow stress and rate of work hardening of quenched and tempered AISI 52100 steel were measured for a variety of heat treatments. Both the flow stress and the work hardening index,n, increase with decreasing tempering temperature. Flow stresses increase initially with increasing austenitizing temperature,T _a, then decrease with a further increase inT _a as the amount of retained austenite increases.n tends to increase asT _a increases. In specimens temperared to eliminate retained austenite,n decreases to near zero as the strain increases. This behavior appears to be characteristic of tempered martensite. When less than 10 pct retained austenite is present,n still decreases with increasing strain, but witn n ore than about 15 pct retained austenite,n increases with strain. Heat treatments which refine the primary carbides increase the flow stress forT _a≤840°C. Since fine primary carbides lead to more retained austenite at a givenT _a, n tends to be greater when primary carbides are refined. For one heat treatment, the retained austenite content was measured by an X-ray method as a function of plastic strain. From changes in the relative intensities of austenite reflections, it was found that austenite crystals most favorably oriented for deformation in compression transform most readily to martensite on straining.     

Role of retained austenite on the deformation of an Fe-0.07 C-1.8 Mn-1.4 Si dual-phase steel

The influence of retained austenite on the work hardening behavior of dual-phase steel has been investigated with an Fe-0.07 C-1.8 Mn-1.4 Si steel. With a constant cooling rate of 5 °C per second after intercritical annealing at 780 °C, a significant quantity (about 8 vol pct) of retained austenite was obtained in the dual-phase microstructure. The retained austenite was classified morphologically into either ‘isolated’ or ‘capsulated’ types by TEM observation. The ‘capsulated’ type, which was found without a particular shape inside the microtwinned martensite particle, withstood much deformation by being protected by the surrounding martensite. While the ‘isolated’ type, which was found with an equiaxed shape and was isolated from martensite particles, was easily deformed by the first several percent plastic strain. The increase in work hardening rate, caused by the strain induced transformation of retained austenite to martensite, was ascribed to the contribution of the ‘isolated’ type, the major volume fraction of retained austenite. The effect of the retained austenite on the yielding of dual-phase steel was not indicated since the reduction in the volume fraction of retained austenite was negligible at the initial deformation stage.     

Modeling tensile deformation of dual-phase steel

An analytical model has been developed which can describe the tensile deformation behavior of dualphase steel containing retained austenite which transforms to martensite during deformation. The model takes into account the internal back stresses created in the material as a result of the deformation. The influence of various metallurgical factors, such as the amounts of the secondary phases (martensite and retained austenite), strength ratio of the phases, work hardening coefficients, and the stability of retained austenite with respect to the strain-induced transformation, was analyzed. The strongest influence on both strength and ductility was found to result from a large work hardening coefficient of the martensite. Increasing the stability of retained austenite to strain-induced transformation improved the ductility remarkably. The model developed was used to predict the tensile deformation behavior of a commercial dual phase steel fairly accurately.     

Characterization of the Carbon and Retained Austenite Distributions in Martensitic Medium Carbon, High Silicon Steel

The retained austenite content and carbon distribution in martensite were determined as a function of cooling rate and temper temperature in steel that contained 1.31 at. pct C, 3.2 at. pct Si, and 3.2 at. pct noniron metallic elements. Mössbauer spectroscopy, transmission electron microscopy (TEM), transmission synchrotron X-ray diffraction (XRD), and atom probe tomography were used for the microstructural analyses. The retained austenite content was an inverse, linear function of cooling rate between 25 and 560 K/s. The elevated Si content of 3.2 at. pct did not shift the start of austenite decomposition to higher tempering temperatures relative to SAE 4130 steel. The minimum tempering temperature for complete austenite decomposition was significantly higher (>650 °C) than for SAE 4130 steel (～300 °C). The tempering temperatures for the precipitation of transition carbides and cementite were significantly higher (>400 °C) than for carbon steels (100 °C to 200 °C and 200 °C to 350 °C), respectively. Approximately 90 pct of the carbon atoms were trapped in Cottrell atmospheres in the vicinity of the dislocation cores in dislocation tangles in the martensite matrix after cooling at 560 K/s and aging at 22 °C. The 3.2 at. pct Si content increased the upper temperature limit for stable carbon clusters to above 215 °C. Significant autotempering occurred during cooling at 25 K/s. The proportion of total carbon that segregated to the interlath austenite films decreased from 34 to 8 pct as the cooling rate increased from 25 to 560 K/s. Developing a model for the transfer of carbon from martensite to austenite during quenching should provide a means for calculating the retained austenite. The maximum carbon content in the austenite films was 6 to 7 at. pct, both in specimens cooled at 560 K/s and at 25 K/s. Approximately 6 to 7 at. pct carbon was sufficient to arrest the transformation of austenite to martensite. The chemical potential of carbon is the same in martensite that contains 0.5 to 1.0 at. pct carbon and in austenite that contains 6 to 7 at. pct carbon. There was no segregation of any substitutional elements.