The role of thermal stabilization in martensite transformations

The variation of the kinetics of the martensite transformation with carbon content and martensite habit plane has been investigated in several Fe−Ni based alloys. Transformation in an Fe-25 wt pct Ni-0.02 wt pct C alloy exhibits predominantly athermal features, but some apparently isothermal transformation also occurs. In a decarburized alloy, on the other hand, the observed kinetic features, such as the dependence ofM _s on cooling rate, were characteristic of an isothermal transformation. In contrast, Fe-29.6 wt pct Ni-10.7 wt pct Co alloys with carbon contents of 0.009 wt pct C and 0.003 wt pct C transform by burst kinetics to {259}_γ plate. At both these carbon levels, theM _b temperatures of the Fe−Ni−Co alloys are independent of cooling rate. It is proposed that the change in kinetic behavior of the Fe-25 pct Ni alloy with the different carbon contents is due to the occurrence of dynamic thermal stabilization in the higher carbon alloy. Dynamic thermal stabilization is relatively unimportant in the Fe−Ni−Co alloys which transform by burst kinetics to {259}_γ plate martensite. P. J. FISHER, formerly with the University of New South Wales D. J. H. CORDEROY, formerly with the University of New South Wales     

Decomposition of Fe-Ni martensite: Implications for the low-temperature (≤500 °C) Fe-Ni phase diagram

The low-temperature (<500 °C) decomposition of Fe-Ni martensite was studied by aging martensitic Fe-Ni alloys at temperatures between 300 °C and 450 °C and by measuring the composition of the matrix and precipitate phases using the analytical electron microscope (AEM). For aging treatments between 300 °C and 450 °C, lath martensite in 15 and 25 wt pct Ni alloys decomposed with γ [face-centered cubic (fcc)] precipitates forming intergranularly, and plate martensite in 30 wt pct Ni alloys decomposed with γ (fcc) precipitates forming intragranularly. The habit plane for the intragranular precipitates is {111}_fcc parallel to one of the {110}_bcc planes in the martensite. The compositions of the γ intergranular and intragranular precipitates lie between 48 and 58 wt pct Ni and generally increase in Ni content with decreasing aging temperature. Diffusion gradients are observed in the matrix α [body-centered cubic (bcc)] with decreasing Ni contents close to the martensite grain boundaries and matrix/precipitate boundaries. The Ni composition of the matrix α phase in decomposed martensite is significantly higher than the equilibrium value of 4 to 5 wt pct Ni, suggesting that precipitate growth in Fe-Ni martensite is partially interface reaction controlled at low temperatures (<500 °C). The results of the experimental studies modify the γ/α + γ phase boundary in the present low-temperature Fe-Ni phase diagram and establish the eutectoid reaction in the temperature range between 400 °C and 450 °C. Formerly Research Assistant, Department of Materials Science and Engineering, Lehigh University     

The relationship between toughness and microstructure in Fe-high Mn binary alloys

The influence of Mn content on the ductile-brittle transition in 16 to 36 wt pct Mn steels was investigated and interpreted in light of the evolving microstructure. It was found that when hcp ε martensite is present in the as-quenched condition or forms during deformation, it lowers the toughness. In 25Mn steel, the stress concentrations at e plate intersections result in the formation of planar void sheets along the {111}_γ planes. The deformation-induced α’ martensite in 16 to 20 pct Mn alloys enhances the toughness, but leads to a ductile-to-brittle transition at low temperatures that is due to the intrusion of an intergranular fracture mode. Binary alloys with greater than 31 pct Mn also fracture in an intergranular mode at 77 K although the impact energy remains quite high. Auger spectroscopy of the fracture surfaces shows no evidence of significant impurity segregation, which suggests the importance of slip heterogeneity in controlling intergranular fracture in these alloys.     

The relationship between toughness and microstructure in Fe-high Mn binary alloys

The influence of Mn content on the ductile-brittle transition in 16 to 36 wt pct Mn steels was investigated and interpreted in light of the evolving microstructure. It was found that when hcp ε martensite is present in the as-quenched condition or forms during deformation, it lowers the toughness. In 25Mn steel, the stress concentrations at e plate intersections result in the formation of planar void sheets along the {111}_γ planes. The deformation-induced α’ martensite in 16 to 20 pct Mn alloys enhances the toughness, but leads to a ductile-to-brittle transition at low temperatures that is due to the intrusion of an intergranular fracture mode. Binary alloys with greater than 31 pct Mn also fracture in an intergranular mode at 77 K although the impact energy remains quite high. Auger spectroscopy of the fracture surfaces shows no evidence of significant impurity segregation, which suggests the importance of slip heterogeneity in controlling intergranular fracture in these alloys.     

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.     

The influence of martensite and ferrite on the properties of two-phase stainless steels having microduplex structures

The mechanical properties of a series of stainless steels ranging in composition from 16.5 pct Cr, 5.5 pct Ni to 23.9 pct Cr, 2.9 pct Ni have been determined. The series of alloys lie along an approximate 1700°F tie line with room temperature microstructures ranging from 100 pct martensite to 100 pct ferrite. Yield and tensile strengths increased directly with increasing martensite content. In alloys containing on the order of 40 to 60 pet martensite, the presence of a fine dispersion of tougher, albeit stronger, martensite was quite effective in lowering the ductile-to-brittle impact transition temperature.     

Martensitic transformations induced by plastic deformation in the Fe-Ni-Cr-C system

Martensitic transformations induced by plastic deformation are studied comparatively in various alloys of three types: Fe-30 pct Ni, Fe-20 pct Ni-7 pct Cr, and Fe-16 pet Cr-13 pct Ni, with carbon content up to 0.3 pct. For all these alloys the tensile properties vary rapidly with temperature, but there are large differences in the value of the temperature rangeM _s toM _d, which strongly increases with substitution of chromium for nickel or with carbon addition. Using the node method, it is found that the intrinsic stacking fault energy in the austenite drastically increases with temperature in all the chromium-bearing alloys investigated. This variation is consistent with the observed influence of temperature on the appearance of twinning or ε martensite during plastic deformation. Very different α’ martensite morphologies can result from spontaneous and plastic deformation induced transformations, especially in Fe-20 pct Ni-7 pct Cr-type alloys where platelike and lath martensites are respectively observed. As in the case of ε martensite, the nucleation process is analyzed as a deformation mode of the material, using a dislocation model. It is then possible to account for the morphology of plastic deformation induced α’ martensite in both Fe-20 pct Ni-7 pct Cr and Fe-16 pct Cr-13 pct Ni types alloys and for the largeM _s toM _d range in these alloys. This paper is based upon a thesis submitted by F. LECROISEY in partial fulfillment of the degree of Doctor of Philosophy at the University of Nancy.     

The non-cubic lattice of rapidly quenched packet martensite

The positions of 200, 020 and 002 peaks of ferrous martensite have been measured individually by a precision X-ray diffractometer technique. Martensite with 18 wt pct Ni and 0.1, 0.2, 0.3, and 0.4 wt pct C was formed by salt-water quenching from preoriented austenite single-crystal slices about 0.5 mm thick. The variations in X-ray peak positions interpreted as changes in lattice parameter yield to the first approximation:Δa/a ₀ = −0.005 [wt pct C],Δb/a ₀ = −0.016 [wt pct C],Δc/a ₀ = −0.037 [wt pct C] for carbon contents between 0.1 and 0.4. For such carbon contents the martensite has packet or mixed packet-lenticular morphology; consequently packet martensite is not cubic as sometimes claimed. Instead its lattice is nearly like that of lenticular martensite with the"a " and"c " parameters varying with carbon content as previously observed for tetragonal martensite, and the" b " parameter unequal to the" a" . The significance of the inequality of the" a " and" b " parameters is unclear, but that inequality appears to be characteristic of some plate and lenticular martensite.     

The effect of grain boundary chemistry on Intergranular stress corrosion cracking of Ni-Cr-Fe alloys in 50 Pct NaOH at 140 °C

The role of chromium, carbon, chromium carbides, and phosphorus on the intergranular stress corrosion cracking (IGSCC) resistance of Ni-Cr-Fe alloys in 50 pct NaOH at 140 °C is studied using controlled-purity alloys. The effect of carbon is studied using heats in which the carbon level is varied between 0.002 and 0.063 wt pct while the Cr level is fixed at 16.8 wt pct. The effect of Cr is studied using alloys with Cr concentrations between 5 and 30 wt pct. The effect of grain boundary Cr and C together is studied by heat-treating the nominal alloy composition of Ni-16Cr-9Fe-0.035C, and the effect of P is studied using a high-purity, P-doped alloy and a carbon-containing, P-doped alloy. Constant extension rate tensile (CERT) results show that the crack depth increases with decreasing alloy Cr content and increasing alloy C content. Crack- ing severity also correlates inversely with thermal treatment time at 700 °C, during which the grain boundary Cr content rises and the grain boundary C content falls. Phosphorus is found to have a slightly beneficial effect on IG cracking susceptibility. Potentiodynamic polarization and potentiostatic current decay experiments confirm that Cr depletion or grain boundary C enhances the dissolution at the grain boundary. Results support a film rupture-anodic dissolution model in which Cr depletion or grain boundary C (independently or additively) enhances dissolution of nickel from the grain boundary region and leads to increased IG cracking.     

The diffusivity of Ni in Fe-Ni and Fe-Ni-P martensites

The diffusivity of Ni in Fe-Ni and Fe-Ni-P martensite, , has been determined between 700 and 300 °C using electron microprobe (EMP) and scanning transmission electron microscope (STEM) techniques. Alloys of various bulk compositions (0 to 30 wt pct Ni, Fe) were homogenized in the single phase austenite (γ-fee) field and quenched to form martensite, α₂ (bcc). Appropriate alloys were tempered isothermally at 300 to 700 °C. The γ nucleated and grew in the parent α₂. The composition of the γ phase and the concentration gradients in the α₂ were measured with the EMP andJor STEM. In order to determine experimentally measured Ni concentration gradients were matched to Ni concentration gradients calculated by a simulation model. The calculated gradients were obtained by solving the appropriate form of Fick’s second law using the Crank-Nicholson numerical technique. The observed diffusivities varied with temperature. Above approximately 410 °C, while below 410°C, = (2.27 × 10⁻¹⁵) exp (− 10,600/RT) cm²/s. The effect of P is to increase the Fe-Ni diffusivities at any temperature by the factor (1 + 1.27C _p + 0.623C _p ² ) whereC _p is the amount of P (wt pct) in α₂. The discontinuous diffusion behavior of is attributable to the high dislocation density of the α₂. Above approximately 410 °C lattice diffusion is dominant while below 410 °C dislocation pipe diffusion is dominant. Formerly Research Assistant in the Department of Metallurgy and Materials Engineering, Lehigh University, Bethlehem, PA     

Structure-property relations and the design of Fe-4Cr-C base structural steels for high strength and toughness

Some design guidelines for improving strength-toughness combinations in medium car-bon structural steels are critically reviewed. From this, quaternary alloy development based on Fe/Cr/C steels with Mn or Ni additions for improved properties is described. Transmission electron microscopy and X-ray analysis reveal increasing amounts of retained austenite in these alloys with Mn content up to 2 wt pct and Ni additions at 5 wt pct after quenching from 1100°C. A corresponding improvement in toughness properties is also found. Grain refining results in a further increase in the amount of retained austenite. In addition, the excellent combinations of strength and toughness in these quaternary alloys are attributed to the production of dislocated lath martensite from a homogeneous austenite phase free from undissolved alloy carbides. The question of thermal instability of retained austenite following tempering is considered in detail and it is shown that the decomposition of retained austenite is closely related to the ease of nucleation and growth of cementite. Thus, graphitizing alloying elements such as Ni are beneficial in postponing the decomposition of retained austenite. Formerly with the Lawrence Berkeley Laboratory, Berkeley, CA This paper is based on a presentation made at a symposium on “Precipitation Processes in Structural Steels” held at the annual meeting of the AIME, Denver, Colorado, February 27 to 28, 1978, under the sponsorship of the Ferrous Metal-lurgy Committee of The Metallurgical Society of AIME.     

Microstructural dependence of Fe-high Mn tensile behavior

The tensile properties of Fe-high Mn (16 to 36 wt pct Mn) binary alloys were examined in detail at temperatures from 77 to 553 K. The Mn content dependence of the deformation and fracture behavior in this alloy system has been clarified by placing special emphasis on the starting microstructure and its change during deformation. In general, the intrusion of hcp epsilon martensite (ε) into austenite (γ) significantly increases the work hardening rate in these alloys by creating strong barriers to further plastic flow. Due to the resulting high work hardening rates, large amounts of e lead to high flow stresses and low ductility. Alloys of 16 to 20 wt pct Mn are of particular interest. While these alloys are thermally stable with respect to bcc α’ martensite formation, 16 to 20 wt pct Mn alloys undergo a deformation induced ε →α’ transformation. The martensitic transformation plays two contrasting roles. The stress-induced ε→ α’ transformation decreases the initial work hardening rate by reducing locally high internal stress. However, the work hardening rate increases as the accumulated α’ laths become obstacles against succeeding plastic flow. These rather complicated microstructural effects result in a stress-strain curve of anomolous shape. Since both the M_s and M_d temperatures for both the ε and α’-martensite transformations are strongly dependent on the Mn content, characteristic relationships between the tensile behavior and the Mn content of each alloy are observed.     

Determination of the Fe-Ni and Fe-Ni-P phase diagrams at low temperatures (700 to 300 °C)

The α + γ two-phase fields of the Fe-Ni and Fe-Ni (P saturated) phase diagrams have been determined in the composition range 0 to 60 wt pet Ni and in the temperature range 700 to 300 °C. The solubility of Ni in (FeNi)₃P was measured in the same temperature range. Homogeneous alloys were austenitized and quenched to form α₂, martensite, then heat treated to formα (ferrite) + γ (austenite). The compositions of the α and γ phases were determined with electron microprobe and scanning transmission electron microscope techniques. Retrograde solubility for the α/(α + γ) solvus line was demonstrated exper-imentally. P was shown to significantly decrease the size of the α + γ two-phase field. The maximum solubility of Ni in α is 6.1 ± 0.5 wt pct at 475 °C and 7.8± 0.5 wt pct at 450 °C in the Fe-Ni and Fe-Ni (P saturated) phase diagrams, respectively. The solubility of Ni in α is 4.2 ± 0.5 wt pct Ni and 4.9 ± 0.5 wt pct Ni at 300 °C in the Fe-Ni and Fe-Ni (P saturated) phase diagrams. Ternary Fe-Ni-P isothermal sections were constructed between 700 and 300 °C. Formerly Research Assistant in Department of Metallurgy & Materials Engineering, Lehigh University, Bethlehem, PA.     

200, 020, and 002 X-ray peaks in tempered Fe-18 Ni-C martensites

Separate 200, 020, and 002 X-ray peaks were recorded for 0.0, 0.4, and 0.8 wt pct carbon (18 pct Ni) martensites after tempering between 25 and 500°C. The carbon bearing martensites studied here have been tempered initially enough to eliminate the “high tetragonality” 002 peak usually recorded for as-quenched martensite and the present results apply to tempered martensite only. The peak maximum is taken to determine the lattice parameter and the peak shape is recorded. At all carbon levels and after all tempering treatments, the “crd parameter is larger than or equal to the “a” or “b”. The relative enlargement is very small (0.08 pct) for the lowest carbon level and for any carbon level after severe tempering (500°C for 15 min). For the two higher carbon alloys tempered at temperatures below 400°C (for 15 min) the “c” parameter is significantly larger than the “a” and “b” and for the 0.4 wt pct C alloy the “b” is significantly smaller than the“a” whereas in the 0.8 pct C alloy the “b” is slightly larger than the “a”. Within experimental error the mean volume of the unit cell does not change during the tempering studied here and is nearly unaffected by the initial carbon content. This indicates that little (at most 0.1 wt pct) carbon is dissolved in tempered martensite. In the low carbon alloy the peaks are symmetric and sharpen symmetrically during tempering. In the higher carbon alloys the peaks are nearly symmetric and sharp after severe tempering. After less severe tempering the 002 peak is asymmetrically broadened toward lower9 values (higher lattice parameters) whereas the 200 and 020 peaks are asymmetrically broadened toward higher 0 values corresponding to lower lattice parameters. This collection of results is tentatively interpreted as being due to strains in martensite due to transformation induced substructure and precipitated carbides.     

Structure and properties of corrosion and wear resistant Cr-Mn-N steels

Steels containing about 12 pct Cr, 10 pct Mn, and 0.2 pct N have been shown to have an unstable austenitic microstructure and have good ductility, extreme work hardening, high fracture strength, excellent toughness, good wear resistance, and moderate corrosion resistance. A series of alloys containing 9.5 to 12.8 pct Cr, 5.0 to 10.4 pct Mn, 0.16 to 0.32 pct N, 0.05 pct C, and residual elements typical of stainless steels was investigated by microstructural examination and mechanical, abrasion, and corrosion testing. Microstructures ranged from martensite to unstable austenite. The unstable austenitic steels transformed to α martensite on deformation and displayed very high work hardening, exceeding that of Hadfield’s manganese steels. Fracture strengths similar to high carbon martensitic stainless steels were obtained while ductility and toughness values were high, similar to austenitic stainless steels. Resistance to abrasive wear exceeded that of commercial abrasion resistant steels and other stainless steels. Corrosion resistance was similar to that of other 12 pct Cr steels. Properties were not much affected by minor compositional variations or rolled-in nitrogen porosity. In 12 pct Cr-10 pct Mn alloys, ingot porosity was avoided when nitrogen levels were below 0.19 pet, and austenitic microstructures were obtained when nitrogen levels exceeded 0.14 pct.     

An investigation of the high-temperature and solidification microstructures of PH 13-8 Mo stainless steel

Differential thermal analysis (DTA), high-temperature water-quench (WQ) experiments, and optical and electron microscopy were used to establish the near-solidus and solidification microstructures in PH 13-8 Mo. On heating at a rate of 0. 33 °C/s, this alloy begins to transform from austenite to δ-ferrite at ≈1350 °C. Transformation is complete by ≈1435 °C. The solidus is reached at ≈1447 °C, and the liquidus is ≈1493 °C. On cooling from the liquid state at a rate of 0. 33 °C/s, solidification is completed as δ-ferrite with subsequent transformation to austenite beginning in the solid state at ≈1364 °C. Insufficient time at temperature is available for complete transformation and the resulting room-temperature microstructure consists of matrix martensite (derived from the shear decomposition of the austenite) and residual δ-ferrite. The residual δ-ferrite in the DTA sample is enriched in Cr (≈16 wt pct), Mo (≈4 wt pct), and Al (≈1. 5 wt pct) and depleted in Ni (≈4 wt pct) relative to the martensite (≈12. 5 wt pct Cr, ≈2 wt pct Mo, ≈1 wt pct Al, ≈9 wt pct Ni). Solid-state transformation of δσ γ was found to be quench-rate sensitive with large grain, fully ferritic microstructures undergoing a massive transformation as a result of water quenching, while a diffusionally controlled Widmanstätten structure was produced in air-cooled samples.     

Microstructure-composition relationships and Ms temperatures in Fe-Cr-Mn-N alloys

Microstructure-composition relationships and M_s temperatures have been determined in high purity nitrided Fe-Cr-Mn alloys, as part of a program to develop improved corrosion-abrasion resistant steels with unstable austenitic microstructures. Compositions in the range 8 to 12 pct Cr, 0 to 10 pct Mn, and 0 to 0.6 pct N were investigated by a resistivity technique to determine M_s temperatures and by X-ray diffraction and metallography to determine constitution. Hardness measurements were also made. At the low alloy end of the range, microstructures after annealing and air cooling are fully martensitic while at the high alloy end they are fully austenitic. At intermediate compositions, mixed martensite-austenite microstructures (with epsilon present as a minor phase in some cases) and unstable austenitic microstructures are obtained. The austenitic alloys contain a high density of stacking faults and the unstable austenitic alloys transform to martensite on deformation. At low N contents (up to at least 0.25 pct N) the M_s-composition relationship is linear and described by: M_s = 555 - 9(Cr - 8) - 40Mn - 450N [1] where M_s is in °C and Cr, Mn, and N are the weight percentages of these elements. At higher N contents, the M_s generally falls more rapidly with increasing nitrogen content. Nitrogen solubility at 1050 °C exceeds about 0.3 pct in all alloys and increases with increasing Cr and Mn content. In commercial purity steels, unstable austenitic microstructures are expected to be obtained in compositions around 10 to 14 pct Cr, 8 to 12 pct Mn, and 0.1 to 0.3 pct N when the total level of these elements is selected to ensure the M_s is below room temperature.     

Microstructure and phase identification in type 304 stainless steel-zirconium alloys

Stainless steel-zirconium alloys have been developed at Argonne National Laboratory to contain radioactive metal isotopes isolated from spent nuclear fuel. This article discusses the various phases that are formed in as-cast alloys of type 304 stainless steel and zirconium that contain up to 92 wt pct Zr. Microstructural characterization was performed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS), and crystal structure information was obtained by X-ray diffraction. Type 304SS-Zr alloys with 5 and 10 wt pct Zr have a three-phase microstructure—austenite, ferrite, and the Laves intermetallic, Zr(Fe,Cr,Ni)_2+x. whereas alloys with 15, 20, and 30 wt pct Zr contain only two phases—ferrite and Zr(Fe,Cr,Ni)_2+x. Alloys with 45 to 67 wt pct Zr contain a mixture of Zr(Fe,Cr,Ni)_2+x and Zr₂(Ni,Fe), whereas alloys with 83 and 92 wt pct Zr contain three phases—α-Zr, Zr₂(Ni,Fe), and Zr(Fe,Cr,Ni)_2+x. Fe₃Zr-type and Zr₃Fe-type phases were not observed in the type 304SS-Zr alloys. The changes in alloy microstructure with zirconium content have been correlated to the Fe-Zr binary phase diagram.     

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.