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Carbon and nitrogen stabilization in stainless steel and its effect on mass transfer in stainless steel niobium one percent zirconium potassium systems
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Martensitic stainless steels find extensive applications due to their optimum combination of strength, hardness and wear-resistance in tempered condition. However, this class of steels is susceptible to embrittlement during tempering if it is carried out in a specific temperature range resulting in significant reduction in toughness. Embrittlement of as-normalised AISI 410 martensitic stainless steel, subjected to tempering treatment in the temperature range of 673–923 K was studied using Charpy impact tests followed by metallurgical investigations using field emission scanning electron and transmission electron microscopes. Carbides precipitated during tempering were extracted by electrochemical dissolution of the matrix and identified by X-ray diffraction. Studies indicated that temper embrittlement is highest when the steel is tempered at 823 K. Mostly iron rich carbides are present in the steel subjected to tempering at low temperatures of around 723 K, whereas chromium rich carbides (M{sub 23}C{sub 6}) dominate precipitation at high temperature tempering. The range 773–823 K is the transition temperature range for the precipitates, with both Fe{sub 2}C and M{sub 23}C{sub 6} types of carbides coexisting in the material. The nucleation of Fe{sub 2}C within the martensite lath, during low temperature tempering, has a definite role in the embrittlement of this steel. Embrittlement is not observed at high temperature tempering because of precipitation of M{sub 23}C{sub 6} carbides, instead of Fe{sub 2}C, preferentially along the lath and prior austenite boundaries. Segregation of S and P, which is widely reported as one of the causes for temper embrittlement, could not be detected in the material even through Auger electron spectroscopy studies. - Highlights: • Tempering behaviour of AISI 410 steel is studied within 673–923 K temperature range. • Temperature regime of maximum embrittlement is identified as 773–848 K. • Results show that type of carbide precipitation varies with temperature of tempering. • Mostly iron rich Fe{sub 2}C carbides are present in the embrittlement temperature range. • With the precipitation of M{sub 23}C{sub 6} carbides, recovery from the embrittlement begins.
Directed energy deposited (DED) and forged austenitic stainless steels possess dissimilar microstructures but can exhibit similar mechanical properties. In this study, annealing was used to evolve the microstructure of both conventional wrought and DED type 304L austenitic stainless steels, and significant differences were observed. In particular, the density of geometrically necessary dislocations and hardness were used to probe the evolution of the microstructure and properties. Forged type 304L exhibited the expected decrease in measured dislocation density and hardness as a function of annealing temperature. Here, the more complex microstructure–property relationship observed in the DED type 304L material is attributed to compositional heterogeneities in the solidification microstructure.
Stainless steels have been exposed to nitric acid solutions containing natural uranium under similar conditions to those found in reprocessing plants. Solution and solid analysis of the stainless steel samples has been undertaken to describe the contamination phenomenon. General corrosion of the surface was seen to take place over the month-long experiments. Contamination has been shown on all exposed surfaces. Solution analysis indicates that an equilibrium state is reached after 2 weeks exposure to the 12 M HNO{sub 3}. Surface analysis through autoradiography and X-ray absorption near edge structure (XANES) indicate that multiple mechanisms of uptake may occur and consequently concentrated regions of contamination may be produced. (authors)
Ferritic-martensitic (FM) steel Grade 92, with or without thermomechanical treatment (TMT), and austenitic stainless steels HT-UPS (high-temperature ultrafine precipitate strengthening) and NF709 were selected as potential candidate structural materials in the U.S. Sodium-cooled Fast Reactor (SFR) program. The objective is to develop advanced steels with improved properties as compared with reference materials such as Grade 91 and Type 316H steels that are currently in nuclear design codes. Composition modification and/or processing optimization (e.g., TMT and cold-work) were performed to improve properties such as resistance to thermal aging, creep, creep-fatigue, fracture, and sodium corrosion. Testings to characterize these properties for the advanced steels were conducted by the Idaho National Laboratory, the Argonne National Laboratory and the Oak Ridge National Laboratory under the U.S. SFR program. This paper focuses on the resistance to thermal aging and creep of the advanced steels. The advanced steels exhibited up to two orders of magnitude increase in creep life compared to the reference materials. Preliminary results on the weldment performance of the advanced steels are also presented. The superior performance of the advanced steels would improve reactor design flexibility, safety margins and economics.
First-Passage Kinetic Monte Carlo (FPKMC) simulations of species migration in duplex stainless steels were performed in order to establish relationships between alloy content, segregation behavior, and the formation of Ni-Si-Mn rich particles in cast duplex stainless steels during thermal aging. The Ni-Si-Mn-rich second phase forms after extended aging at reactor operating temperatures and degrades alloy properties. Simulations of Ni-Si-Mn cluster formation were validated through comparison with experimental results obtained through Atom Probe Tomography (APT) on similar alloy compositions, identifying several trends. First, Cu promotes the formation of Ni-Si-Mn clusters, but only when Ni or Mn prefer segregation to the surface of Cu particles; without the segregation of these species, the critical composition for the clusters to form was not achieved. Second, the width of precipitate-denuded zones near ?/d interfaces increases with decreasing Cu content. This finding was in strong agreement with APT results, further validating our model. Finally, our model predicts that Ni-Si-Mn cluster formation will be the most extensive when the Si:Mn ratio is approximately 1:1 and the least extensive when one of these key elements is less concentrated (Mn = 0.5 at.% or Si = 0.5 at.%). The implications of these results on how to improve alloy properties are discussed.
Austenitic stainless steels are the standard materials for containment of hydrogen and tritium because of their resistance to mechanical property degradation in those environments. The mechanical performance of the primary containment material is critical for tritium handling, processing, and storage, thus comprehensive understanding of the processes of tritium embrittlement is an enabling capability for fusion energy. This work describes the investigation of the effects of low levels of tritium-decay-helium ingrowth on 304 L tubes. Long-term aging with tritium leads to high helium contents in austenitic stainless steels and can reduce fracture toughness by 95 %, but the details of behavior at low helium contents are not as well characterized. Here, we present results from tensile testing of tritium pre-charged 304 L tube specimens with a variety of starting microstructures that all contain a low level of helium. The results of the tritium exposed-and-aged materials are compared to previously reported results on similar specimens tested in an unexposed condition as well as the hydrogen precharged condition. Tritium precharging and aging for a short duration resulted in increased yield strengths, ultimate tensile strengths and slightly increased elongation to failure, comparable to higher concentrations of hydrogen precharging.
Gas phase hydrogen permeation studies were conducted on hollow, cylindrical membranes of triply zone-refined alpha iron, AISI 304 austenitic stainless steel, and AISI-SAE 4130 steel in both the normalized (ferrite and carbide) and quenched and tempered (martensite) conditions. Membrane temperature was varied from less than 100 C to near 600 C and hydrogen pressure was varied. For one membrane material, normalized 4130 steel, gas phase hydrogen transport under both steady state and nonsteady state conditions was demonstrated to be controlled by lattice diffusion. Additionally, Sievert's law was shown to be applicable. For all membrane materials, expressions for the coefficients for hydrogen permeation were determined by analysis of steady state transport; the coefficients for diffusion were determined by the lag time technique applied to nonsteady state transport; and through a knowledge of the Sievert's constants, the subsurface equilibrium lattice hydrogen concentrations were determined.
Competing microstructural evolution mechanisms can exist simultaneously when duplex stainless steels are operating for several decades in a high temperature service environment. Such competition between different microstructural evolution pathways can be difficult to ascertain using simple model alloy systems necessitating detailed structural and compositional analysis of phase transformation mechanisms in complex alloys Thus, in this study duplex stainless steels with complex but well understood chemistries were used to investigate the relative importance of different heterogeneous nucleation sites – specifically spinodal decomposition and Cu clustering – on precipitation of Ni-Si-Mn particles during long term thermal aging. Precipitation of Ni-Si-Mn particles in duplex stainless steels and ferritic steels during thermal aging and irradiation is known to have profound effect on mechanical properties. Using duplex stainless steels with custom modified compositions along with atom probe tomography characterization and first-passage kinetic Monte Carlo (FPKMC) simulations it is revealed that while the interface between Cr and Fe formed during spinodal decomposition can be a pathway for diffusion of Ni, Si, Mn, and Cu, it is not a site that encourages precipitation of Ni-Si-Mn rich particles. Instead, the presence of a higher concentration of Cu in these steels leads to formation of small Cu clusters with high energy interfaces that act as nucleation sites for Ni-Si-Mn particles because of its strong interaction particularly with Ni increasing the chemical driving force for precipitation. These results will help inform predictive models for the use of duplex stainless steels and other precipitation-hardened alloys for extended operation at high temperatures.
Ferritic stainless steels are promising candidates for IT-SOFC interconnect applications due to their low cost and resistance to oxidation at SOFC operating temperatures. However, steel candidates face several challenges; including long term oxidation under interconnect exposure conditions, which can lead to increased electrical resistance, surface instability, and poisoning of cathodes due to volatilization of Cr. To potentially extend interconnect lifetime and improve performance, a variety of surface treatments were performed on AISI 441 ferritic stainless steel coupons prior to application of a protective spinel coating. The coated coupons were then subjected to oxidation testing at 800 and 850°C in air, and electrical testing at 800°C in air. While all of the surface-treatments resulted in improved surface stability (i.e., increased spallation resistance) compared to untreated AISI 441, the greatest degree of improvement (through 20,000 hours of testing at 800°C and 14,000 hours of testing at 850°C) was achieved by surface blasting.
Austenitic stainless steels are subject to the precipitation of chromium carbides (M 23 C 6 ) during exposure to high temperatures, causing these alloys to be susceptible to intergranular corrosion due to chromium depletion along grain boundaries. The acoustic nonlinearity parameter, β, shows sensitivity to the formation of carbides in these alloys. The Thermo-Calc TC-PRISMA module was used to model the nucleation and growth of grain boundary M 23 C 6 carbides. The model was verified with scanning transmission electron microscopy analysis that allowed measurements of the grain boundary precipitates. The paper introduces a reduced-order model of the acoustic nonlinearity based on the formation of misfit dislocations at the interface of the grain boundary precipitate and matrix to explain the change in β during isothermal aging. Furthermore, a direct relationship between the radius of the M 23 C 6 grain boundary carbides and β was observed and verified with nonlinear ultrasound measurements on 304L and 316L stainless steels.
Future technologies require structural alloys resistant to corrosion in supercritical CO 2 (sCO 2 ) fluids containing impurities such as H 2 O and O 2 . Traditional pipeline steels are potentially unsuitable for these environments and more corrosion resistant alloys such as stainless steels might be required. Little is known about the corrosion products formed on, and hence the processes which control corrosion of, stainless steels in impure sCO 2 environments. In this study, austenitic stainless steel 347H (UNS S34709) was exposed to sCO 2 containing H 2 O and O 2 at 8 MPa and 50°C or 250°C, and separately to the aqueous phase in equilibrium with the sCO 2 at 50°C, to simulate conditions expected in sCO 2 -based power cycles and carbon capture and storage pipelines. Only thin (< 20 nm) surface films formed after 500 h resulting in small mass changes and corrosion rates < 10 –4 mm/y, suggesting the material resists significant degradation in these environments. X-ray photoelectron spectroscopy and transmission electron microscopy were used to characterize the corrosion films in detail. Here, the exposure to the aqueous phase resulted in a thin (< 5 nm) Cr-oxide and/or -hydroxide passive film, while exposure to sCO 2 phases resulted in a multilayer Fe-rich oxide structure characteristic of a gas-phase oxidation process.
In this study, the role of minor alloying additions in 347H stainless steels (UNS34709, ASTM A240/240M) on creep-rupture properties at 650-750°C and microstructure evolution during isothermal exposure at 750°C has been investigated, aiming to provide the experimental dataset as boundary conditions of physics-based modeling for material/component life prediction. Four different 347H heats containing various amounts of boron and nitrogen additions were prepared and evaluated. The combined additions of B and N are found to stabilize the strengthening secondary M23C6 carbides and retarding the transition from M23C6 to sigma phase precipitates during thermal exposure. The observed kinetics of microstructure evolution reasonably explains the improvement of creep-rupture properties of 347H stainless steels with the B and N additions.
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Radiation induced segregation (RIS) is a well-studied phenomena which occurs in many structurally relevant nuclear materials including austenitic stainless steels. RIS occurs due to solute atoms preferentially coupling to mobile point defect fluxes that migrate and interact with defect sinks. Here, a 304 stainless steel was neutron irradiated up to 47.1 dpa at 320 °C. Investigations into the RIS response at specific grain boundary types were utilized to determine the sink characteristics of different boundary types as a function of irradiation dose. A rate theory model built on the foundation of the modified inverse Kirkendall (MIK) model is proposed and benchmarked to the experimental results. This model, termed the GiMIK model, includes alterations in the boundary conditions based on grain boundary structure and includes expressions for interstitial binding. This investigation, through experiment and modeling, found specific grain boundary structures exhibit unique defect sink characteristics depending on their local structure. Such interactions were found to be consistent across all doses investigated and had larger global implications including precipitation of Ni-Si clusters near different grain boundary types.
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This dataset contains files used to perform the microstructure simulations in the manuscript "A two-phase cellular automata model of grain structure in laser powder bed fusion-processed stainless steel", data analysis scripts, and experimental data used for comparison purposes, in Acta Materialia