Thermodynamics of carbon in austenite and Fe-Mo austenite

A Cahn Electrobalance has been used to determine directly and very accurately the carbon content of iron, iron-0.48 wt pct molybdenum and iron-1.16 wt pct molybdenum specimens which were equilibrated with a series of methane-hydrogen gas mixtures of constant composition. The equilibria investigated involved the austenite phases of the alloys at 783, 813 and 848‡C. The experimental results permit direct calculation of the activities of carbon in the samples, relative to graphite as unity, and of the enthalpy and entropy of solution of carbon. The results are compared with the experimental measurements of a number of other investigators. The results are in excellent agreement with those of Smith and Schenck and Kaiser for the Fe-C system at 800‡C, and indicate -H _C ^/M values of 9700 ± 500 cal/mole for pure Fe, 10,030 ± 500 cal/mole for an Fe-0.48 wt pct Mo alloy, and 10,150 ± 500 cal/mole for an Fe-1.16 wt pct Mo alloy. The effect of molybdenum in austenite is to decrease the activity coefficient of carbon in austenite.     

Thermodynamics and solubility of carbon in ferrite and ferritic Fe-Mo alloys

A Cahn Electrobalance has been used to determine directly and very accurately the carbon content of α-Fe, Fe-0.48 wt pct Mo and Fe-1.16 wt pct Mo specimens which were equilibrated with a series of methane-hydrogen gas mixtures. The equilibria investigated involved the ferrite phases of the alloys between 682 and 848‡C. The experimental results permitted direct calculation of the activities of carbon in the samples, relative to graphite as unity, and of other thermodynamic functions, without the necessity for any correction factors. The results have been compared with the experimental measurements of a number of other investigators. In ferrite, the partial molar enthalpy and entropy of solution of carbon are found to be 26,800 cal/mole, (112, 130 J/mole), and 30.59 cal/K-mole, (127.99 J/K-mole) respectively at temperatures below about 727‡C. Above this temperature, the values are 25,200 cal/mole and 29.13 cal/K-mole, respectively. The addition of molybdenum results in an increase in these properties below 727‡C and a decrease in the values above 753‡C, and the changes are found to be proportional to the molybdenum content. The solubility of carbon in α-Fe is found to be 0.0176 wt pct at the eutectoid temperature. Molybdenum increases the solubility relative to the Fe-C system at temperatures above the eutectoid and decreases it below the eutectoid.     

On the microstructure and mechanical behavior of melt-spun Fe-24 pct Ni-0.5 pct C Ribbons: Effect of austenite grain size

The role of carbon on the retention and decomposition of austenite in a melt-quenched Fe-24 wt pct Ni-0.5 wt pct C alloy made by the melt-spinning method has been investigated, using a combination of X-ray diffractometry, optical and TEM metallography, microhardness measurements, and tensile tests. It is found that the addition of 0.5 wt pct C to Fe-24 wt pct Ni alloy leads to retention of austenite to a temperature close to -196 °C, when the alloy is quenched from the melt. The austenite grain size varies from ∼0.2 μm to ∼2 μm on going from the wheel to the gas side. The cooling rate, accordingly, changes from 5 × 10⁷ to 4 × 10⁴ Ks^-1. The changes in the mechanical properties have been correlated with the accompanying changes in the ribbon microstructure. The Central Metallurgical Research and Development Institute, National Research Centre, Dokki, Cairo, Egypt     

Diffusion and electrotransport of carbon in γ-phase iron-nickel alloys

The diffusivity and electrotransport behavior of carbon in an iron-32.5 wt pct nickel alloy was investigated for the temperature range of 1220 to 1415 K for two carbon concentrations. The electrical resistivity was measured as a function of temperature between room temperature and 1625 K for carbon contents of 0.002, 0.10, and 0.21 wt pct. Values for the activation energy for diffusion of 32.0 ± 5.8 and 36.0 ± 5.2 kcal per mole were determined for alloys containing 0.10 and 0.21 wt pct carbon respectively, with slightly smaller values being found for the activation energy for electrotransport. The sign of the effective valence indicates that carbon migrates toward the cathode.     

Investigation into the effect of substituting Mo by W on the behavior,during aging,of the maraging type ternary alloys

The substitution of W for Mo in the Fe-16.4 Ni-8.2 Mo alloys produces a dual component alloy: i) lath martensite containing 5 wt pet W and ii) 2 pct intermetallic phase, the composition of which is 33.3 Fe-4.4 Ni-62.3 W. The behavior of the two alloys Fe-16.4 Ni-8.2X (X)=Mo or W) is compared during heating (between 20 and 950°C) at a rate of 300°C/h. For both alloys, the martensite transforms into austenite in three successive steps by a predominantly diffusional mechanism. The behavior of the two alloys in similar during isothermal aging at temperatures less than or equal to 550°C. In fact, the aging process takes place in three successive stages which are studied using the small-angle X-ray scattering technique and electron microscopy.     

Strength of initially virgin martensites at - 196 °C after aging and tempering

The compressive strength at -196°C of martensites in Fe-0.26 pct C-24 pct Ni, Fe-0.4 pct C-21 pct Ni, and Fe-0.4 pct C-18 pct Ni-3 pct Mo alloys, all with subzero M temperatures, has been determined in the virgin condition and after one hour at temperatures from -80 to +400 °C. The effects of ausforming (20 pct reduction in area of the austenite by swaging at room temperature prior to the martensitic transformation) were also investigated. For the unausformed martensites, aging at temperatures up to 0 °C results in relatively small increases in strength. Above 0 °C, the age hardening increment increases rapidly, reaching a maximum at 100 °C. Above 100 °C, the strength decreases continuously with increasing tempering temperature except for the molybdenum-containing alloy, which exhibits secondary hardening on tempering at 400 °C. For the ausformed martensites, the response to aging at subzero temperatures is greater than for unausformed material. Strength again passes through a maximum on aging at 100 °C. However, on tempering just above 100 °C, the ausformed materials show a slower rate of softening than the unausformed martensites. The strengthening produced by the ausforming treatment is largest for the Fe-0.4 pct C-18 pct Ni-3 pct Mo alloy, but there is no evidence of carbide precipitation in the deformed austenite to a°Count for this effect of molybdenum.     

The isothermal decomposition of austenite in Fe−Mo−C alloys

High purity iron alloys containing molybdenum and carbon have been isothermally transformed in the range 600° to 900°C and the structures examined optically and in the electron microscope. The decomposition of the austenite commences at the grain boundaries forming two different ferrite/carbide morphologies. Predominantly, fine fibers of Mo₂C, 300 to 500Å diam, grow in association with ferrite and in contact with the austenite, forming characteristic nodules. Increasing the carbon content from 0.2 to 1.0 wt pct results in a change in structure during transformation from Mo₂C fibers/ferrite to a typical coarse pearlite reaction. In addition, Mo₂C nucleates repeatedly at the moving λ-α phase boundary to form sheets of particles about 200 to 400Å apart, the individual acicular particles being about 50Å diam in the early stages of precipitation.     

Effects of austenitizing temperature on the kinetics of the proeutectoid ferrite reaction at constant austenite grain size in an Fe-C alloy

Austenitizing an Fe-0.23 pct C alloy at 1300°C and further at 900°C prior to isothermal transformation was found to increase the growth kinetics of grain boundary ferrite allotriomorphs while decreasing their rate of nucleation. A scanning Auger microprobe was used to establish that sulfur segregates to the austenite grain boundaries and does so increasingly with decreasing austenitizing temperature. A binding free energy of sulfur to these boundaries of approximately 13 kcal/mole (54.4 kj/mole) was calculated from theMcLean adsorption isotherm. The kinetic results were explained in terms of preferential reduction of the austenite grain boundary energy decreasig nucleation kinetics, and adsorption of sulfur at α:γ boundaries increasing the carbon concentration gradient in austenite driving growth.     

Estimation of nucleation rate and growth rate from time dependence of global microstructural properties during phase transformations

An approach has been developed for calculating nucleation and growth rates from the time variation of the volume fraction, surface area, and integral mean curvature of the product phase during a phase transformation. The local growth rate of the product phase can be estimated without any assumption or knowledge regarding the nucleation behavior. The approach is applicable over the complete range of volume fractions(i.e., from zero to one). Practical feasibility of the approach has been demonstrated by deducing the nucleation and growth rates of austenite during austenitization of pearlite in an Fe-0.83 wt pct C alloy at 730 ‡C, 740 ‡C, and 750 ‡C. It is concluded that the local growth rate and nucleation rate of austenite remain constant during an isothermal austenitization of pearlite. Formerly with the Department of Metallurgical Engineering, Indian Institute of Technology, Kanpur, India     

Carbon Diffusion Measurement in Austenite in the Temperature Range 500 °C to 900 °C

Carbon diffusion in austenite plays a critical role in phase transformation in steel. However, it can only be estimated in the fully austenitic range and has then to be extrapolated to the temperature range of the phase transformation. Therefore, published data are limited to temperatures above 750 °C. In this study, new experiments are carried out to determine the carbon diffusion coefficient in austenite at temperatures as low as 500 °C. Carburization experiments are performed in the austenitic range for a Fe-1.5 pct Mn 0.13 pct C and a Fe-31 pct Ni alloy (wt pct). Composition profile measurements, which are done using glow discharge optical emission spectrometry (GDOES), show that the surface composition is not constant with time. A methodology has been developed to assess the diffusion coefficient of carbon in austenite combining the measured carbon profiles and a numerical method to compute the diffusion profile taking into account the time evolution of the boundary condition. This method is first validated on the Fe-C-Mn steel. Carburization experiments are carried out on a Fe-31 pct Ni alloy at 900 °C, 800 °C, 700 °C, 600 °C, and 500 °C. The carbon diffusion coefficient is assessed using the method described above and fitted with the following expression (T in Kelvin): \( D = 1.23\cdot10^{{ - 6}} \cdot e^{{ - \frac{{15,050}} {{T{\left( {\text{K}} \right)}}}}} ({\text{m}}^{{\text{2}}} {\text{/s}}) \). The new expression is compared with previous experimental results measured for comparable nickel content at higher temperatures, and it shows a reasonable agreement. The model proposed by Ågren for carbon diffusion has been modified to take into account the thermodynamic contribution of nickel. This model also shows good agreement with the present experimental results, even if it was fitted to experiments performed at higher temperatures.     

Nanocrystallization and magnetic properties of Fe-30 weight percent Ni alloy by surface mechanical attrition treatment

A nanostructured surface layer was formed in Fe-30 wt pct Ni alloy by surface mechanical attrition treatment (SMAT). The microstructure of the surface layer after SMAT was investigated using optical microscopy, X-ray diffraction, and transmission electron microscopy. The analysis shows that the nanocrystallization process at the surface layer starts from dislocation tangles, dislocation cells, and subgrains to highly misoriented grains in both original austenite and martensite phases induced by strain from SMAT. The magnetic properties were measured for SMAT Fe-30 wt pct Ni alloy. The saturation magnetization (M _s ) and coercivity (H _c ) of the nanostructured surface layers increase significantly compared to the coarse grains sample prior to SMAT. The increase of M _s for SMAT Fe-30 wt pct Ni alloy was attributed to the change of lattice structure resulting from strain-induced martensitic transformation. Meanwhile, H _c was further increased from residual microstress and superfined grains. These were verified by experiments on SMAT pure Ni and Co metal as well as liquid nitrogen-quenched Fe-30 wt pct Ni alloy.     

Strength of Initially Virgin Martensites at — 196 °C after Aging and Tempering

The compressive strength at —196°C of martensites in Fe-0.26 pct C-24 pct Ni, Fe-0.4 pct C-21 pct Ni, and Fe-0.4 pct C-18 pct Ni-3 pct Mo alloys, all with subzero M_s temperatures, has been determined in the virgin condition and after one hour at temperatures from —80 to +400 °C. The effects of ausforming (20 pct reduction in area of the austenite by swaging at room temperature prior to the martensitic transformation) were also investigated. For the unausformed martensites, aging at temperatures up to 0 °C results in relatively small increases in strength. Above 0 °C, the age hardening increment increases rapidly, reaching a maximum at 100 °C. Above 100 °C, the strength decreases continuously with increasing tempering temperature except for the molybdenum-containing alloy, which exhibits secondary hardening on tempering at 400 °C. For the ausformed martensites, the response to aging at subzero temperatures is greater than for unausformed material. Strength again passes through a maximum on aging at 100 °C. However, on tempering just above 100 °C, the ausformed materials show a slower rate of softening than the unausformed martensites. The strengthening produced by the ausforming treatment is largest for the Fe-0.4 pct C-18 pct Ni-3 pct Mo alloy, but there is no evidence of carbide precipitation in the deformed austenite to account for this effect of molybdenum. This paper is based on a presentation made at the “Peter G. Winchell Symposium on Tempering of Steel” held at the Louisville Meeting of The Metallurgical Society of AIME, October 12-13, 1981, under the sponsorship of the TMS-AIME Ferrous Metallurgy and Heat Treatment Committees.     

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     

Thermal processing of ferritic 5Mn steel for toughness at cryogenic temperatures

It is shown that a thermal treatment which combines grain refinement with an intercritical temper (the 2BT treatment) may be used to achieve a promising combination of strength and toughness in a nickel-free ferritic steel of nominal composition Fe-5Mn-0.2Mo-0.04C at temperatures as low as -196 °C. The properties achieved are attributed to a symbiotic influence between the grain refinement treatment and the introduction of thermally stable retained austenite during intercritical tempering, a conclusion supported by a comparison of the results to those obtained with simpler heat treatments. The influence of carbon, manganese, and nickel additions to the base compositions are studied. An increase in carbon content above 0.04 wt pct causes a deterioration in toughness, as does an increase in manganese to 8 wt pct. An addition of 1 to 3 wt pct nickel is beneficial giving an increase in alloy strength at -196 °C without loss of toughness. Formerly Visiting Scientist, Lawrence Berkeley Laboratory.     

Continuous cooling transformation kinetics of thermomechanically worked low-carbon austenite

Continuous cooling transformation diagrams were determined for molybdenum-boron steels containing 0.24, 0.4, and 0.66 pct Mo with 0.1 pct C, and also 0.4 pct Mo with 0.2 pct C, after thermomechanically working by compressive deformation to 12, 25, and 50 pct reduction at 830°C (1525°F), as well as for the steels in the underformed condition. In underformed specimens, higher carbon or molybdenum decreased the limiting cooling rate for the avoidance of polygonal ferrite formation. The same was true for deformed specimens, although increased deformation raised the limiting cooling rates of all compositions. The limiting cooling rate for polygonal ferrite formation increased exponentially with austenite, deformation, as measured by true strain. Thermomechanical working also raised bainite start temperatures at fast cooling rates and caused small increases in martensite start temperatures.     

Dynamic recrystallization during creep in a 45 Pct Ni-35 pct Fe-20 pct Cr alloy system

A combined 3.5 wt pct Mo + 1.2 wt pct Ti imparted dynamic recrystallization in a 35 wt pct Fe-45 wt pct Ni-20 wt pct Cr alloy system during creep at 700 °C, whereas 3.5 wt pct Mo addition alone did not initiate recrystallization. Dynamic recrystallization substantially increased the creep elongation and produced a high ductile fracture topography in the present alloy system. A subgrain coalescence nucleation mechanism for dynamic recrystallization mechanism was operative during creep. The critical initiation strain requirements are also discussed.     

Effects of alloying elements upon austenite decomposition in Low-C steels

The kinetics of austenite decomposition were studied in high-purity Fe-0.1C-0.4Mn-0.3Si-X (concentrations in weight percent;X represents 3Ni, 1Cr, or 0.5Mo) steels at temperatures between 500 °C and 675 °C. The transformation stasis phenomenon was found in the Fe-C-Mn-Si-Mo and Fe-C-Mn-Si-Ni alloys isothermally transformed at 650 °C and 675 °C but not in the Fe-C-Mn-Si and Fe-C-Mn-Si-Cr alloys at any of the temperatures investigated. The occurrence of transformation stasis was explained by synergistic interactions among alloying elements. The paraequilibrium model was applied to calculate the metastable fraction of ferrite in each alloy. This fraction was shown to coincide with cessation of transformation in the Mo alloy transformed at 600 °C. Transformation stasis was found in both the Ni and the Mo alloys isothermally reacted at 650 °C and 675 °C. The interactions among Mn, Si, and Mo, as well as interactions among Mn, Si, and Ni, appear to decrease the threshold concentrations for transformation stasis in Fe-C-Mn-Si systems. Segregation of Mn and Mo to the α/yγ boundary, assisted by the presence of Si, was suggested to enhance the solute draglike effect (SDLE) and lead to transformation stasis. In the Ni alloy, a lower driving force for ferrite formation resulting from the Ni addition could be responsible for the occurrence of transformation stasis.     

The effect of titanium on creep strength in 2.25 Pct Cr-1 Pct Mo steels

The effect of a low level of titanium on the microstructure and creep properties of 2.25 pct Cr-1 pct Mo steels has been examined as a function of carbon content and austenitizing temperature. The addition of 0.04 wt pct titanium resulted in a dramatic increase in creep strength at 565 °C, and this was found to be associated with the presence in the microstructure of very small (50 to 100 Å) titanium-bearing precipitates based upon both TiC and Mo₂C. The variation of the minimum creep rate with carbon content and austenitizing treatment was explained in terms of the solubility of TiC in austenite. The titanium-bearing carbides have an important effect on microstructural stability and on the maintenance of creep strength, but it is also apparent that solid solution strengthening by molybdenum can make a significant contribution to creep strength at low carbon levels (0.02 wt 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.     

Nucleation sites for ultrafine ferrite produced by deformation of austenite during single-pass strip rolling

An austenitic Ni-30 wt pct Fe alloy, with a stacking-fault energy and deformation characteristics similar to those of austenitic low-carbon steel at elevated temperatures, has been used to examine the defect substructure within austenite deformed by single-pass strip rolling and to identify those features most likely to provide sites for intragranular nucleation of ultrafine ferrite in steels. Samples of this alloy and a 0.095 wt pct C-1.58Mn-0.22Si-0.27Mo steel have been hot rolled and cooled under similar conditions, and the resulting microstructures were compared using transmission electron microscopy (TEM), electron diffraction, and X-ray diffraction. Following a single rolling pass of ∼40 pct reduction of a 2mm strip at 800 °C, three microstructural zones were identified throughout its thickness. The surface zone (of 0.1 to 0.4 mm in depth) within the steel comprised a uniform microstructure of ultrafine ferrite, while the equivalent zone of a Ni-30Fe alloy contained a network of dislocation cells, with an average diameter of 0.5 to 1.0 μm. The scale and distribution and, thus, nucleation density of the ferrite grains formed in the steel were consistent with the formation of individual ferrite nuclei on cell boundaries within the austenite. In the transition zone, 0.3 to 0.5 mm below the surface of the steel strip, discrete polygonal ferrite grains were observed to form in parallel, and closely spaced “rafts” traversing individual grains of austenite. Based on observations of the equivalent zone of the rolled Ni-30Fe alloy, the ferrite distribution could be correlated with planar defects in the form of intragranular microshear bands formed within the deformed austenite during rolling. Within the central zone of the steel strip, a bainitic microstructure, typical of that observed after conventional hot rolling of this steel, was observed following air cooling. In this region of the rolled Ni-30Fe alloy, a network of microbands was observed, typical of material deformed under plane-strain conditions.