Behavior of grain boundary chemistry and precipitates upon thermal treatment of controlled purity alloy 690

Grain boundary composition and carbide composition and structure were characterized for various microstructures of controlled purity alloy 690. Heat treatments produced varying degrees of grain boundary chromium depletion and precipitate distributions which were characterizedvia scanning transmission electron microscopy (STEM). Convergent beam electron diffraction revealed that the dominant carbide is M₂₃C₆, and energy dispersive X-ray analysis (EDAX) determined that the metallic content was about 90 at. pct chromium. A discontinuous precipitation reaction was observed and is attributed to a high degree of carbon supersaturation. Grain boundary composition measurements confirm that chromium depletion is controlled by volume diffusion of chromium to chromium-rich grain boundary carbides in the temperature range of 873 to 1073 K. Grain boundary chromium levels as low as 18.8 at. pct were obtained by thermal treatment at 873 K for 250 hours and 973 K for 1 hour. A thermodynamic and kinetic model developed for alloy 600 was modified to describe the development of the chromium depletion profile in alloy 690 during thermal treatment. Experimentally measured chromium profiles agree well with the model results for the dependence of the chromium depletion zone width and depth on various input parameters. The establishment of the model for alloy 690 allows the chromium depletion zone width and depth to be computed as a function of alloy composition, grain size, and temperature. The chromium depletion profiles and the precipitate structure and composition of controlled purity 690 are compared to those of controlled purity 600. A thermodynamic analysis of the carbide stability indicates that other factors, such as favorable orientation relationships, play an important role in controlling the precipitation of Cr₂₃C₆ in nickel-base alloys.     

Experimental Investigation and Analytical Prediction of σ-Phase Precipitation in AISI 316L Austenitic Stainless Steel

The phase precipitation in industrial AISI 316L stainless steel during aging for up to 80,000 hours between 823 K and 1073 K (550 °C and 800 °C) has been studied using transmission electron microscopy, scanning transmission electron microscopy, and carbon replica energy-dispersive X-ray microanalysis. Three phases were identified: Chromium carbides (M₂₃C₆), Laves phase (η), and σ-phase (Fe-Cr). M₂₃C₆ carbide precipitation occurred firstly and was followed by the η and σ-phases at grain boundaries when the aging temperature is higher than 873 K (600 °C). Precipitation and growth of M₂₃C₆ create chromium depletion zones at the grain boundaries and also retard the σ-phase formation. Thus, the σ-phase is controlled by the kinetic of chromium bulk diffusion and can appear only when the chromium reaches, at grain boundaries and at the M₂₃C₆/γ and M₂₃C₆/η/γ interfaces, content higher than a critical value obtained by self-healing. An analytical model, based on equivalent chromium content, has been established in this study and successfully validated to predict the time–temperature–precipitation diagram of the σ-phase. The obtained diagram is in good agreement with the experimental results.     

Microstructure of a Creep-Resistant 10 Pct Chromium Steel Containing 250 ppm Boron

The microstructure of a trial martensitic chromium steel containing a high content of boron (250 ppm) was characterized in detail in the as-tempered and aged conditions. This steel has a similar composition and heat treatment as the TAF steel that still is unsurpassed in creep strength among all 9 to 12 pct chromium steels. Characterization was performed by using scanning electron microscopy, energy-filtered transmission electron microscopy, secondary ion mass spectroscopy, and atom probe tomography. Focus was placed on investigating different types of precipitates that play a key role in improving the creep resistance of these steels. The low tempering temperature of 963 K (690 °C) is enough for the precipitation of the full volume fraction of both MX and M₂₃C₆. A high boron content, more than 1 at. pct, was found in M₂₃C₆ precipitates and they grow slowly during aging. The high boron level in the steel results in metal borides rather than BN with the approximate formula (Mo_0.66Cr_0.34)₂(Fe_0.75V_0.25)B₂. Two families of MX precipitates were found, one at lath boundaries about 35 nm in size and one dense inside the laths, only 5 to 15 nm in size.     

Quantification of precipitates in advanced creep resistant 9-12% Cr steels

In this paper a procedure is introduced for the quantification of precipitates appearing in 9-12°Cr-steels. Results gained from conventional transmission electron microscopic (TEM) investigations are compared with results from energy filtering transmission electron microscopic (EFTEM) investigations. The study was performed on a creep rupture specimen of the cast material G-X12CrMoWVNbN10-1-1 exposed at 600°C and ruptured after 33000 h. The size distribution of M₂₃C₆ carbides, MX phase and Laves phase were measured for both the un-stressed head and the stressed shank (gauge length) part of the investigated specimen. In particular, problems and sources of uncertainty concerning the quantitative determination of particle parameters in this type of steel are discussed. It is shown that quantification of the MX-particles by means of TEM bright field images is hardly possible. The size distributions of M₂₃C₆ carbides and MX phase overlap significantly which makes a separation based only on their size nearly impossible. Only Laves phase occupies a different size range. The difference between the size distributions of head and shank is pronounced only for M₂₃C₆ carbides. The measured particle distributions obey more closely a log-normal distribution rather than a normal distribution.     

Evolution of Precipitates of S31042 Heat Resistant Steel During 700 °C Aging

The evolution of precipitates of S31042 steel during 700 °C aging was investigated by using a scanning electron microscope, a transmission electron microscope, and electron energy spectrum technology. The various combinations of M₂₃C₆, MX, NbCrN, and σ and G phases in the steel were found at different aging states. In the beginning of aging, M₂₃C₆ precipitates swiftly along the grain boundaries. When the aging time exceeds 6000 h, precipitated M₂₃C₆ carbides along the grain boundaries turn to be granular. It was found that Si element segregates to grain boundaries during above process, which may enhance the granular shape of M₂₃C₆ carbides and its transformation to σ and G phases. When the aging time exceeds 10000 h, various shaped σ phase and granular G phase appear along the grain boundaries and there are no continuous M₂₃C₆ carbides along the grain boundaries. Meanwhile, a large quantity of granular M₂₃C₆ carbides and a minor amount of G phase precipitate near the grain boundaries. Based on the segregation of silicon to the grain boundaries, a precipitation evolution model during aging was concluded.     

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

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

Phase transformations during aging of a nitrogen-strengthened austenitic stainless steel

An analytical electron microscopy study was undertaken in order to characterize intergranular and matrix precipitation accompanying intermediate temperature aging in NITRONIC 50, a nitrogen-strengthened austenitic stainless steel. Extensive precipitation on most grain boundaries had occurred after aging for 24 hours at 675 °C. The primary intergranular phase at that time was Cr-rich M₂₃C₆, and energy dispersive spectra taken on grain boundary segments between these carbides indicated Cr-depletion and Fe- and Ni-enhancement relative to the matrix. After aging for 336 and 1008 hours at 675 °C, M₆C (eta-carbide) precipitates were also present on grain boundaries. These precipitates were distinguished from M₂₃C₆ on the basis of their lattice parameters and chemistries, with M₆C containing less Cr and Fe, and more Ni, Mo, and Si than M₂₃C₆. The differences in chemistry were clarified by a statistical treatment of the spectra. The statistical analysis also showed that precipitates with a range of chemistries between M₂₃C₆ and M₆C coexisted with these phases on the grain boundaries. Associated with this shift in precipitate stoichiometry was an increase in the average concentration of Cr and a decrease in the average concentration of Ni at the grain boundaries. Intergranular sigma phase was also observed after times 24 hours at 675 °C, with sigma precipitating on grain boundaries containing carbides. Intragranular precipitates observed to be stable up to 1008 hours at 675 °C included Z-phase, a complex nitride which had formed during solution annealing; M₇C₃ carbides, which nucleated at Z-phase/austenite interfaces; M₂₃C₆ carbides, which precipitated on incoherent twin boundaries; and Cr-rich MN precipitates, which nucleated on dislocations.     

Calculation and evaluation of the gibbs energies of formation of Cr3C2, Cr7C3, and Cr23C6

A thermodynamic analysis of chemical composition data for a series of iron alloys containing chromium and carbon has been completed. These data were obtained from literature compilations for alloys equilibrated for extended times at 700 °C under neutral atmospheres. The results of this analysis, when supplemented with thermochemical data from the literature, permitted the calculation of the standard Gibbs energies of formation for the chromium carbides Cr₇C₃ and Cr₂₃C₆ over the range 600 to 1000 °C. These standard Gibbs energies were compared to data for these carbides from other sources. Available Gibbs energy data for the third pure chromium carbide, Cr₃C₂, were also evaluated. For each of these three compounds, a separation of the values for the Gibbs energy of formation into two distinct groups was observed. Each of these groups can be classed according to the nature of the experimental study used, whether it be a high temperature solid-gas equilibration involving a system of a carbide-chromic oxide-carbon (or chromium) with carbon monoxide, on one hand, or a series of investigations concerned mainly with electrolytic cell measurements, plus the work on which the present study is based. It is suggested that the differences in the Gibbs energies of formation for the respective carbides are associated with 1) the nonstoichiometric nature of these carbides and 2) possible dissolution of oxygen in the carbides during the equilibration studies.     

Effect of carbon concentration on precipitation behavior of M<Subscript>23</Subscript>C<Subscript>6</Subscript> carbides and MX carbonitrides in martensitic 9Cr steel during heat treatment

The distributions and precipitated amounts of M₂₃C₆ carbides and MX-type carbonitrides with decreasing carbon content from 0.16 to 0.002 mass pct in 9Cr-3W steel, which is used as a heat-resistant steel, has been investigated. The microstructures of the steels are observed to be martensite. Distributions of precipitates differ greatly among the steels depending on carbon concentration. In the steels containing carbon at levels above 0.05 pct, M₂₃C₆ carbides precipitate along boundaries and fine MX carbonitrides precipitate mainly in the matrix after tempering. In 0.002 pct C steel, there are no M₂₃C₆ carbide precipitates, and instead, fine MX with sizes of 2 to 20 nm precipitate densely along boundaries. In 0.02 pct C steel, a small amount of M₂₃C₆ carbides precipitate, but the sizes are quite large and the main precipitates along boundaries are MX, as with 0.002 pct C steel. A combination of the removal of any carbide whose size is much larger than that of MX-type nitrides, and the fine distributions of MX-type nitrides along boundaries, is significantly effective for the stabilization of a variety of boundaries in the martensitic 9Cr steel.     

Compression characteristics of 6Cr21Mn10MoVNbN heat resistant valve alloy at elevated temperatures

Abstract

6Cr21Mn10MoVNbN is a new type of alloy used for heavy duty engines. Thermal simulation, metallography, X-ray diffraction and theoretical analysis have been used to study the deformation behaviour of the alloy at elevated temperatures. By introducing an internal variable parameter, a constitutive equation has been suggested for the dynamic calculation of the stress/strain curve for this alloy based on the Zerrilli–Armstrong equation used for fcc materials. The data calculated using the equation developed agree fairly well with the experimental data. The microstructure of the alloy is found to depend greatly on temperature and strain rate. When the alloy is deformed at 850°C, Cr₂₃C₆ precipitates from the matrix. The lower the strain rate, the more Cr₂₃C₆ precipitated from the matrix. At the same time, the amount of Cr₂₃C₆ decreases with increasing temperature. Between 850 and 1050°C, the amount of NbN in the alloy increases with increasing temperature and reaches a peak at 1050°C. NbN begins to decrease when the temperature gets to 1150°C. At this temperature, carbides and nitrides in the alloy, especially those distributed on the grain boundaries, begin to be dissolved into the matrix in great deal. The microcracks propagate easily along the grain boundaries of the alloy.     

Carbide precipitation in 12Cr1MoV power plant steel

The chemistry and other characteristics of carbide precipitates in 12CrlMoV steel of the type used in the power generation industry were studied using energy dispersive X-ray spectroscopy and electron and X-ray diffraction techniques, and the results have been compared against thermodynamic calculations. As a result of the much larger substitutional solute concentrations present in the alloy, unlike the carbides that occur in steels containing smaller concentrations of chromium and molybdenum, it is found that the equilibrium M₂₃C₆ carbide precipitates very rapidly during heat treatments of the kind used routinely for stress-relief purposes. The chemical compositions of carbides therefore do not change much during subsequent service at elevated temperatures.     

A Study of Submicron Grain Boundary Precipitates in Ultralow Carbon 316LN Steels

This article reports our efforts in characterization of an ultralow carbon 316LN-type stainless steel. The carbon content in the material is one-third that in a conventional 316LN, which further inhibits the formation of grain boundary carbides and therefore sensitizations. Our primary effort is focused on characterization of submicron size precipitates in the materials with the electron backscatter diffraction (EBSD) technique complemented by Auger electron spectroscopy (AES). Thermodynamic calculations suggested that several precipitates, such as M₂₃C₆, Chi, Sigma, and Cr₂N, can form in a low carbon 316LN. In the steels heat treated at 973 K (700 °C) for 100 hours, a combination of EBSD and AES conclusively identified the grain boundary precipitates (≥100 nm) as Cr₂N, which has a hexagonal closed-packed crystallographic structure. Increases of the nitrogen content promote formation of large size Cr₂N precipitates. Therefore, prolonged heat treatment at relatively high temperatures of ultralow carbon 316LN steels may result in a sensitization.     

Influence of thermal aging on the intergranular corrosion resistance of types 304LN and 316LN stainless steels

Intergranular corrosion (IGC) resistance of types 304LN and 316LN stainless steels (SS) thermally aged at 823, 873, and 923 K for various durations was assessed by ASTM A262 practice A test (electrolytic etch test) and electrochemical potentiodynamic reactivation (EPR) test. The results indicated that the type 316LN SS has significantly improved IGC resistance compared to 304LN SS. Based on the results of these tests, time-temperature-sensitization (TTS) diagrams were developed for both alloys. The secondary precipitates formed during thermal aging treatments were electrochemically extracted and analyzed by X-ray diffraction (XRD) to determine the types of precipitates formed during the aging treatments. The results indicated that the precipitates were mostly of M₂₃C₆ carbides.     

Instabilities in stabilized austenitic stainless steels

The effect of aging on the precipitation of grain boundary phases in three austenitic stainless steels (AISI 347, 347AP, and an experimental steel stabilized with hafnium) was investigated. Aging was performed both on bulk steels as well as on samples which were subjected to a thermal treatment to simulate the coarse grain region of the heat affected zone (HAZ) during welding. Aging of the bulk steels at 866 K for 8000 hours resulted in the precipitation of Cr₂₃C₆ carbides, σ, and Fe₂Nb phases; the propensity for precipitation was least for the hafnium-stabilized steel. Weld simulation of the HAZ resulted in dissolution of the phases present in the as-received 347 and 347AP steels, leading to grain coarsening. Subsequent aging caused extensive grain boundary Cr₂₃C₆ carbides and inhomogeneous matrix precipitation. In addition, steel 347AP formed a precipitate free zone (PFZ) along the grain boundaries. The steel containing hafnium showed the best microstructural stability to aging and welding. Formerly with Exxon Research and Engineering Company.     

Carbide Transformations during Aging of Wear-Resistant Cobalt Alloys

Wear-resistant cobalt-based alloys were thermally aged for 30, 300, and 1000 hours at 650°C and 850°C in vacuum sealed tubes of silica. Unidirectional solidification was used to promote coarser structures easier to investigate. The precipitates were characterized by scanning and transmission electron microscopy, X-ray diffraction, and microprobe analysis. During aging secondary M₂₃C₆ transforms into M₆C. Concomitantly, the primary carbides undergo internal transformation from M₇C₃ to M₆C, and M₆C loses carbon and becomes M₁₂C. Three main findings are reported: (1) a correlation between the nature of precipitates and the chemical segregations, (2) modification of the composition, the morphology, and the crystallographic structure of the carbides, and (3) in these alloys M₂₃C₆ is only an intermediate phase thermodynamically unstable.     

High-temperature thermodynamic properties of the chromium carbides determined using the torsion-effusion technique

The pressures of carbon monoxide in equilibrium with a Cr₂₃C₆-Cr₂O₃-Cr mixture and with a Cr₇C₃-Cr₂O₃-Cr₂₃C₆ mixture have been measured in the temperature range 1100 to 1300 K using the torsion-effusion technique. From the equilibrium data, the following equation for ΔG^of of Cr₂₃C₆ (in cal per mole) has been calculated: ΔG _f ° (±1200) = −77,000 - 18.3T (1150 to 1300 K) Combining the results of this study at temperatures between 1100 and 1300 K with those of Kelleyet al., ³ at temperatures between 1500 and 1720 K, the following equation for ΔG^of of Cr₇C₃ (in cal per mole) has been determined: ΔG _f ° (±400) = −35,200 - 8.7T (1100 to 1720 K) ) The above equation for ΔG^of of Cr₇C₃ has been used to re-evaluate the equilibrium data of Kelleyet al., ³ and the following equation for ΔG^of of Cr₃C₂ (in cal per mole) has been obtained: ΔG _f ° (±400) = −16,400 - 4.4T (1300 to 1500 K) CHROMIUM reacts with carbon to form three carbides:^1,2 Cr₂₃C₆, Cr₇C₃, and Cr₃C₂. The chromium carbides are of considerable technical importance because of their precipitation behavior in certain high-chromium steels and superalloys. A precise knowledge of their thermodynamic properties is essential for the understanding and the prediction of their chemical behavior in various environments. This paper is based upon a thesis submitted by A. D. KULKARNI in partial fulfillment of the requirements of the degree of Doctor of Philosophy at the University of Pennsylvania.     

M5C2 Carbides in a High-Chromium Ferritic/Martensitic Steel

The precipitate phases in an 11 pct Cr ferritic/martensitic steel normalized at 1323 K (1050 °C) for 0.5 hour and tempered at 1053 K (780 °C) for 1.5 hours have been investigated. Except for dominant phases, Cr-rich M₂₃C₆ carbide and Nb-rich, Ta-Nb-rich, and V-rich MC carbides, needle-like precipitates with a typical size of 70 to 310 and 10 to 30 nm for the length of the long and short axis of the needles, respectively, were also observed on the extraction carbon replica of the steel. The typical metallic element composition of the needle-like precipitates is about 53-82Fe, 14-26Cr, 0.5-18Ta, 1-6W, and 2-5Co in atomic pct. Through energy dispersive X-ray analysis and electron diffraction along with calculations regarding lattice parameter and interplanar spacing, the needle-like precipitates were identified as a Fe-rich M₅C₂ carbide, which is not known to have been reported previously in high-chromium steels. The M₅C₂ carbide has a base-centered monoclinic crystal structure with the approximate lattice parameters a/b/c = 1.142/0.5186/0.5383 nm and β = 104.68 deg. The formation of the Fe-rich M₅C₂ carbides in the steel has been discussed. The effect of chromium content in matrix and boron addition on the precipitate phases in ferritic/martensitic steels has also been discussed.     

Chromium depletion in the vicinity of carbides in sensitized austenitic stainless steels

The analytical electron microscope (AEM) was used to examine the microstructure of type 316LN stainless steel alloys which had been annealed for 50 to 300 hours in the temperature range 600 to 700 °C. The M₂₃C₆ carbide chemistry and distribution are described as a function of heat treatment.X-ray spectroscopy in the AEM revealed significant chromium depletion at grain boundaries in the vicinity of carbides for samples aged at 50 and 100 hours at 650 °C and 100 and 300 hours at 700 °C, with lower grain boundary chromium values observed at 650 °C than at 700 °C. The width of the chromium depleted zone normal to the grain boundaries increased with increasing annealing time and/or temperature. Measurements of chromium concentration along the grain boundaries away from a carbide were made after aging at 700 °C for 100 hours, and the chromium level rose steadily until the bulk value was reached at a distance of ~3μm from the carbide. The width of the chromium depleted zone normal to the boundaries in the same sample was an order of magnitude less. Some molybdenum depletion was also found at the grain boundaries, and the Mo-depletion profiles were in form and extent similar to the chromium results. Simple thermodynamic models were used to calculate the equilibrium value of chromium at the carbide-matrix interface, and the chromium distribution along and normal to the grain boundaries. The results of these models agreed well with the AEM results, and the agreement can be improved by considering the effect of electron probe configuration on the AEM measurements. The calculated thermodynamic data and the AEM results were related to the corrosion behavior of the alloys. The occurrence of severe asymmetries in some concentration profiles normal to the grain boundaries, which increased with increasing annealing temperature or time, was shown to be due to boundary movement during the discontinuous precipitation of M₂₃C₆ carbides.     

Thermodynamics of the carbides in the system Fe-Cr-C

Phase relations in the Fe-Cr-C system in the temperature range 900 to 1150°C have been studied using metallographic and X-ray methods and the electron microprobe. An isothermal section of the phase diagram at 1000°C is shown. Lattice dimensions of the three carbides were determined for several values of the ratio Cr:(Fe +Cr). The solubilities of the carbides at each temperature were determined by metallographic study of quenched specimens. The distribution of Cr between austenite (γ) and the several carbides was determined by use of the electron microprobe. Data of Wada et al on the activity of carbon were used to calculate activities at the y-phase boundary and the free energy of the several carbides as a function of their chromium content. The data are treated thermodynamically on the basis of assumed random mixing of Cr and Fe atoms in each carbide. While this randomness was not definitely proved, the assumption was shown to be reasonable and the results useful. Extrapolation to 0 and 100 pct Cr gives values for the standard free energy of Cr₇C₃ and the hypothetical carbides Cr₃₆C, and Fe₇C₃. Formerly with the Research Staff, Massachusetts Institute Technology