A theoretical analysis of the spinodal decomposition in Fe- C martensite during aging stage of tempering

A thermodynamic model of Fe-C martensite is proposed, which has a distinct physical meaning and is easily treated mathematically (high order derivation). When applying this model to the spinodal decomposition in Fe-C martensite during aging, the theoretical values (critical compositions, sizes of products) are in good agreement with experimental data. The miscibility gap of Fe-C martensite is set up. From this diagram, it is clear that spinodal decomposition may affect the later stages of tempering of medium and high carbon steels. Finally, the discussion shows that A1, A2 stages of aging are both spinodal decomposition, but to different extents.     

The clustering and coarsening of carbon multiplets during the aging of martensite from mössbauer spectroscopy: The preprecipitation stage of epsilon carbide

Mössbauer spectra of as-quenched and aged martensite (9.5 at. pct C) are analyzed in terms of seven Fe environments, the abundances of which evolve with aging time. Besides the atoms of the matrix (A), Fe atoms which are first nearest neighbors of an isolated interstitial can only be distinguished by their quadrupole shift depending upon whether they lie in a direction perpendicular (B _a) or parallel to thec axis (B _c); classC atoms have two carbon neighbors whileD orE belong to an ordered phase; classF atoms have three carbon neighbors. The carbon multiplet model, based on interstitials residing exclusively in octahedral sites, an elastic stability of theC-C 1/2«111” doublet and a diffusion path for carbon in (001)α' can explain all the features observed: a first step attributed to the clustering of isolated multiplets, and a second step to the coarsening into extended multiplets which leads to the emergence of a new ordered iron carbide (B2 monoclinic with parallelepiped cell of 5.73, 6.74, and 8.60 Å) which transformsin situ into ε-carbide (~Fe₉C₄) (η carbide as long as it is coherent with the matrix). The positions of carbon atoms in Fe₉C₄ are specified and a synopsis with related phenomena is drawn.     

The effect of the first and second stages of tempering on microcracking in martensite of an Fe-1.22 C alloy

The effect of tempering on microcracking in the plate martensite of an Fe-1.22 C alloy was investigated by isothermal heat treatments in the temperature range between 180 and 225°C. The second stage of tempering, followed by X-ray measurement of retained austenite, was confirmed to depend upon the diffusion of C in austenite, and the transformation product was found to consist of very closely spaced cementite lamellae in ferrite. Microcracking, despite the volume expansion that accompanies the transformation of the retained austenite, decreased only slightly with time during the second stage. The major decrease in microcracking occurred during the first stage, a result attributed to the plastic deformation that accompanies the dimensional changes caused by the reduction of the lattice tetragonality of the high carbon martensite in the first stage. Metallographic observations of surface relief and etching effects associated with martensite plates provided evidence of the first-stage plastic flow. The authors were formerly Research Assistant and Professor, respectively at Lehigh University, Bethlehem, PA.     

The morphology,crystallography, and mechanism of carbide precipitation in an Fe-0.12 Pct C-3.28 Pct Ni alloy

Carbide precipitation during the eutectoid decomposition of austenite has been studied in an Fe-0.12 pct C-3.28 pct Ni alloy by transmission electron microscopy (TEM) supplemented by optical microscopy. Nodular bainite which forms during the latter stages of austenite decomposition at 550 °C exhibits two types of carbide arrangement: (a) banded interphase boundary carbides with particle diameters of about 20 to 90 nm and mean band spacings between 180 and 390 nm and (b) more randomly distributed (“nonbanded”) elongated particles exhibiting a wide range of lengths between 33 and 2500 nm, thicknesses of approximately 11 to 50 nm, and mean intercarbide spacings of approximately 140 to 275 nm. Electron diffraction analysis indicated that in both cases, the carbides are cementite, obeying the Pitsch orientation relationship with respect to the bainitic ferrite. The intercarbide spacings of both morphologies are significantly larger than those previously reported for similar microstructures in steels containing alloy carbides other than cementite (e.g., VC, TiC). Both curved and straight cementite bands were observed; in the latter case, the average plane of the interphase boundary precipitate sheets was near {110}_α//{011}_c consistent with cementite precipitation on low-energy {110}_α//{111}_γ ledge terrace planes (where α,β, andc refer to ferrite, austenite, and cementite, respectively). The results also suggest that the first stage in the formation of the nonbanded form of nodular bainite is often the precipitation of cementite rods, or laths, in austenite at the α:γ interfaces of proeutectoid ferrite secondary sideplates formed earlier. Although these cementite rods frequently resemble the “fibrous” microstructures observed by previous investigators in carbide-forming alloy steels, they are typically much shorter than fibrous alloy carbides. The bainitic microstructures observed here are analyzed in terms of a previously developed model centered about the roles of the relative nucleation and growth rates of the product phases in controlling the evolution of eutectoid microstructures.     

Mössbauer spectroscopy study of the aging and tempering of high nitrogen quenched Fe-N alloys: Kinetics of formation of Fe16N2 nitride by interstitial ordering in martensite

The distribution of nitrogen atoms in austenite and during the different stages of aging and tempering of martensite is studied by Mössbauer spectroscopy, X-ray diffraction, and transmission electron microscopy (TEM). Transmission Mössbauer spectroscopy (TMS) and conversion electron Mössbauer spectroscopy (CEMS) are used for studying the austenite phase where the distribution of nitrogen atoms is found to depend on the nitriding method, gas nitriding in our case, or ion implantation. Conversion electron Mössbauer spectroscopy, which concerns a depth predominantly less than 200 nm, reveals a nitrogen atom distribution different from that found in the bulk by TMS. The identification and kinetics of the stages of aging and tempering of martensite are followed by TMS measurements, and the phase characterization is confirmed by X-ray diffraction and TEM. The major stages are the early ordering of nitrogen atoms, which leads to small coherent precipitates of α-Fe₁₆N₂; the passage by thickening to semicoherent precipitates of α-Fe₁₆N₂; the dissolution of α-Fe₁₆N₂ with the concomitant formation of /gg’-Fe₄N; and the decomposition of retained austenite by tempering. The three first stages correspond to activation energies of 95, 126, and 94 kJ/mole, respectively, consistent with the nitrogen diffusion for the first and third stages and the dislocation pipe diffusion of iron for the second.     

The morphology and substructure of {225}F martensite in an Fe−Mn−Cr−C alloy

A transmission electron microscopy and diffraction study of martensite plates in an Fe-3 pct Mn-3 pct Cr-1 pct C alloy was carried out with particular attention to details of the martensite substructure. A corresponding optical metallographic study of plate morphology was made. A variability in martensite substructure was observed from plate to plate, although a (252)_F ^* plate was generally associated with (112)_B transformation twins and {111}_F stacking faults. The particular (111)_F fault variant gave rise to a wedge-shaped plate morphology. Planar {101}_B inhomogeneities were frequently observed in the martensite, and most of these appear to be derived from austenite stacking faults. In general, more than one type of inhomogeneity was observed in a single martensite plate and the “typical” plate substructure was rather difficult to characterize, although the habit plane was found invariably to be (252)_F.     

Discussion of “spinodal decomposition during aging of Fe-Ni-C martensites” and structure of the Fe6C carbide

K.A TAYLOR, L. CHANG, G.B. OLSON, G.D.W. SMITH, M. COHEN, and J.B. VANDER SANDE:Metall. Trans. A, 1989, vol. 20A, pp. 2717–37.     

The effect of structure on the deformation of as-quenched and tempered martensite in an Fe-0.2 pct C alloy

As-quenched and tempered martensite in an Fe-0.2 pct C alloy were subjected to tensile testing and structural characterization by light and transmission electron microscopy. The light temper, 400°C-l min, did not change packet morphology, but did reduce dislocation density, coarsen lath size and cause the precipitation of carbides of a variety of sizes. The yield strength of the as-quenched martensite was strongly dependent upon packet size according to a Hall-Petch relationship, but tempering significantly diminished the packet size dependency, a result attributed to packet boundary carbide precipitation and the attendant elimination of carbon segregation present in the as-quenched martensite because of autotempering. Examination of thin foils from strained tensile specimens showed that a well-defined cell structure developed in the as-quenched martensite, but that the random distribution of jogged dislocations and carbide particles produced by tempering persisted on deformation of the tempered specimens. The authors were formerly Research Assistant and Professor, respectively, at Lehigh University, Bethlehem, PA.     

An investigation of the effects of austenite strength and austenite stacking fault energy on the morphology of martensite in Fe-Ni-Cr-0.3C alloys

The relative effects of austenite stacking fault energy and austenite yield strength on martensite morphology have been investigated in a series of three Fe-Ni-Cr-C alloys. Carbon content (0.3 wt pct) andM ₆ temperature (− 15°) were held constant within the series. Austenite yield strength atM _s was measured by extrapolating elevated temperature tensile data. Austenite stacking fault energy was measured by the dislocation node technique. Martensite morphologies were characterized by transmission electron microscopy and electron diffraction techniques. A transition from plate to lath martensite occurred with decreasing austenite stacking fault energy. The austenite yield strength atM _s for the low SFE, lath-forming alloy was found to be higher than previously reported for lath-forming alloys. The relative effects of these variables on martensite morphologies in these alloys is discussed.     

On the substructure of athermal and isothermal martensites formed in an Fe-21 Ni-4mn alloy

Transmission electron microscopy and diffraction analysis have been made on the athermal and isothermal martensites formed in an Fe-21Ni-4Mn alloy, with particular attention to details of the martensite crystallography and substructure. In general, a variation in the martensite substructure has been found, comparing adjacent regions of near proximity in the same specimen, but nevertheless general conclusions can be drawn. Plates of martensite were observed after both isothermal and athermal treatment. At an early stage of growth, the isothermal martensite plates exhibit similar crystallographic and substructural features compared to those found in the athermally formed plates. In both cases, the overall macroscopic martensite habit plane is near (252)_f, but such macroscopic plates actually consist of many small plates (termed subplates) of the same orientation with a (121)_f habit plane. In the case of isothermal plates an apparent rotation of the habit plane to ward ( 111 )_f occurs as the plates thicken. This rotation was not observed for athermally formed plates. The observations made in this work suggest that temperature dependent relaxation of transformation strains may affect the growth and autocatalytic nucleation of martensite subplates, thus causing the microstructural differences occurring between isothermal and athermal martensite plates. Formerly with the Department of Metallurgy and Mining Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 Formerly with the Department of Metallurgy and Mining Engineering, University of Illinois     

The influence of grain boundary precipitation on the measurement of chromium redistribution and phosphorus segregation in Ni-16Cr-9Fe

The redistribution of chromium at the grain boundary and the segregation of phosphorus to the grain boundary in Ni-16Cr-9Fe is measured following thermal treatment at 700 °C for 1 to 100 hours. The addition of carbon to the base alloy results in the formation of Cr₇C₃ precipitates at the grain boundary and the formation of a chromium depleted zone in the adjacent matrix. Measurement of the Cr concentration is affected by the presence of Cr-rich carbides, and a technique of ratioing the Auger signal of the element of interest to a sum of the signals of elements present in the carbide and the matrix is required to minimize the scatter in the data. The presence of carbides does not affect the kinetics or extent of phosphorus segregation to the grain boundary, and there is no evidence of co-segregation of phosphorus with any major alloying element. The free energy of segregation of phosphorus is determined to be 46.2 KJ/mole at 1100 °C and 40.8 KJ/mole at 700 °C. Results show that the intergranular fracture path is along the carbide-matrix interface as opposed to through the carbides or some distance into the matrix. These results permit the calculation of the coverage of the grain boundary with carbides.     

Creep and low-cycle fatigue behavior of ferritic Fe-24Cr-4Al alloy in the dynamic strain aging regime: Effect of aluminum addition

Creep and low-cycle fatigue behavior of ferritic Fe-24Cr-4Al alloy was studied in the temperature range of 673 to 873 K, where dynamic strain aging (DSA) occurrence was found. The DSA of the alloy manifested in the form of serrated flow, negative strain rate sensitivity, and the peak or plateau in the variations of yield strength (YS) and ultimate tensile strength (UTS) with temperature. The characteristic creep behavior of the alloy was experimentally verified as that for a class I solid solution. However, this ferritic alloy showed an anomalous high stress exponent (n=5.7) and high activation energy (Q _c =285 kJ/mol) of the secondary creep, which were commonly exhibited by class II solid solutions. During cyclic deformation, the alloy displayed serration in the stress-strain hysteresis loops, increased cyclic hardening, and enhanced planarity of dislocations. On the basis of the observed experimental results and proper analysis, it was proposed that there was strong elastic interaction between solute aluminum atoms and dislocations in the DSA temperature domain. The anomalous creep and fatigue features were interpreted in terms of the interaction of aluminum with the dislocations.     

Isolation of carbon and grain boundary carbide effects on the creep and intergranular stress corrosion cracking behavior of Ni−16Cr−9Fe−xC alloys in 360 °C primary water

The influence of carbon and grain boundary carbides on intergranular stress corrosion cracking (IGSCC) of controlled-purity Ni−16Cr−9Fe−xC alloys in 360 °C primary water was investigated using constant load tensile (CLT) and constant extension rate tensile (CERT) tests. The CLT test results confirmed that carbon in solution decreases the creep rate by several orders of magnitude, while grain boundary carbides serve to increase the creep susceptibility. Although carbon increases the work hardening rate, it is demonstrated, using the Bailey-Orowan creep model, that the primary effect of carbon in solution is to delay the recovery process of climb at the grain boundary, thereby reducing the creep rate. Grain boundary carbides produce a negligible contribution to the internal stress and may increase the creep rate by acting as dislocation sources. Grain boundary carbide precipitation increases IGSCC resistance in 360 °C primary water containing 0, 1, and 18 bar hydrogen, providing the highest overall resistance to both environmentally induced creep and cracking. The magnitude of the beneficial effect of grain boundary carbides is extremely sensitive to hydrogen overpressure, with the largest influence observed for 1 bar hydrogen. The detrimental effect of hydrogen on IGSCC shows consistencies with aspects of both film rupture/slip dissolution and hydrogen embrittlement models. J.L. HERTZBERG, formerly Graduate Student Research Assistant, Department of Materials Science and Engineering, University of Michigan     

Induction of differentiation in normal human keratinocytes by adenovirus-mediated introduction of the eta and delta isoforms of protein kinase C

Protein kinase C (PKC) plays a crucial role(s) in regulation of growth and differentiation of cells. In the present study, we examined possible roles of the alpha, delta, eta, and zeta isoforms of PKC in squamous differentiation by overexpressing these genes in normal human keratinocytes. Because of the difficulty of introducing foreign genes into keratinocytes, we used an adenovirus vector system, Ax, which allows expression of these genes at a high level in almost all the cells infected for at least 72 h. Increased kinase activity was demonstrated in the cells overexpressing the alpha, delta, and eta isoforms. Overexpression of the eta isoform inhibited the growth of keratinocytes of humans and mice in a dose (multiplicity of infection [MOI])-dependent manner, leading to G1 arrest. The eta-overexpressing cells became enlarged and flattened, showing squamous cell phenotypes. Expression and activity of transglutaminase 1, a key enzyme of squamous cell differentiation, were induced in the eta-overexpressing cells in dose (MOI)- and time-dependent manners. The inhibition of growth and the induction of transglutaminase 1 activity were found only in the cells that express the eta isoform endogenously, i.e., in human and mouse keratinocytes but not in human and mouse fibroblasts or COS1 cells. A dominant-negative eta isoform counteracted the induction of transglutaminase 1 by differentiation inducers such as a phorbol ester, 1alpha,25-dihydroxyvitamin D3, and a high concentration of Ca2+. Among the isoforms examined, the delta isoform also inhibited the growth of keratinocytes and induced transglutaminase 1, but the alpha and zeta isoforms did not. These findings indicate that the eta and delta isoforms of PKC are involved crucially in squamous cell differentiation.     

On the Relation of Microstructure and Texture Evolution in an Austenitic Fe-28Mn-0.28C TWIP Steel During Cold Rolling

In the present study, microstructure and texture evolution in an austenitic Fe-28 wt pct Mn-0.28 wt pct C TWIP steel in the range between 10 and 80 pct reduction by cold rolling were systematically analyzed. The formation of the observed microstructural features occurred in three different stages: I (10 to 20 pct)—mainly slip lines, grain elongation, and formation of few twin-matrix lamellae; II (30 to 50 pct)—severe increase of the volume fraction of twins, alignment of twins with the rolling plane, and formation of microshear bands; and III (60 to 80 pct)—further alignment of twins, evolution of a herring bone structure, and macroshear bands. In contrast to most f.c.c. metals, the transition from Copper- to Brass-type texture occurred at low strain levels (30 pct). This behavior is attributed to the early formation of deformation twins in the material and can be related to the SFE of this high manganese steel. At higher reduction levels, microscopic (≥40 pct) and macroscopic shear band formation (≥60 pct) contributed to the increase of randomly oriented grains, mainly at the expense of the Brass component. Furthermore, the formation of the Goss component and of the 〈111〉//ND fiber (γ) is attributed to severe twin formation.