Studies on Nb Microalloying of 13Cr Super Martensitic Stainless Steel

The effect of Nb microalloying on microstructure, mechanical properties, and pitting corrosion properties of quenched and tempered 13?pct Cr-5?pct Ni-0.02?pct C martensitic stainless steels with different Mo and N contents was investigated. The microstructure, density, and dispersion of high-angle boundaries, nanoscale precipitates, and amount of retained austenite were characterized by using electron backscattered diffraction, transmission electron microscopy, and X-ray diffraction to correlate with properties. The results show that the combined effects of lowering nitrogen content in 13?pct Cr-5?pct Ni-1~2?pct Mo-0.02?pct C steels to 0.01?wt pct, and adding 0.1?pct Nb are to decrease the amount of Cr-rich precipitates, as Nb preferentially combines with residual carbon and nitrogen to form carbonitrides, suppressing the formation of Cr₂N and Cr₂₃C₆. Austenite grain refinement can be achieved by Nb microalloying through proper heat treatment. If the nitrogen content is kept high, then Cr-rich precipitates would occur irrespective of microalloying addition. The NbN would also occur at high temperature, which will act as substrate for nucleation of coarse precipitates during subsequent tempering, impairing the toughness of the steel. It was shown that the addition of Nb to low interstitial super martensitic stainless steel retards the formation of reversed austenite and results in the formation of nanoscale precipitates (5 to 15?nm), which contribute to a significant increase in strength. More importantly, the pitting corrosion resistance was found to increase with Nb addition. This is attributed to suppression of Cr-rich precipitates, which can cause local depletion of Cr in the matrix and the initiation of pitting corrosion.     

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.     

Novel hafnium containing steels for power generation

Abstract

There is clear evidence that creep damage in power plant steels is associated with grain boundary precipitates. These particles provide favourable nucleation sites for grain boundary cavities and microcracks. The formation of M₂₃C₆ carbides as grain boundary precipitates can also lead to grain boundary chromium depleted zones which are susceptible to corrosive attack. Such precipitates are the causing loss of creep life in the later stages of creep because of their very high coarsening rate. Through Monte Carlo based grain boundary precipitation kinetics models, combined with continuum creep damage modelling it is predicted that improvements in creep behaviour of power plant steels can be achieved by increasing the proportion of MX type particles. Studies of a Hf containing steel have produced improvements in both creep and corrosion properties of 9%Cr steels. Hf has been ion implanted into thin foils of a 9 wt-%Cr ferritic steel to study its effect on precipitation. Two new types of precipitates are formed, Hf carbide, (an MX type precipitate) and a Cr–V rich nitride, with the formula M₂N. The Hf carbide particles were identified using convergent beam diffraction techniques, and micro-analysis. The nanosized particles are present in much higher volume fractions when compared to VN volume fractions in conventional power plant ferritic steels. Furthermore it is confirmed that the Hf causes the removal of M₂₃C₆ grain boundary precipitates. This has led to an increased concentration of Cr within the matrix, reduced chromium depleted zones at grain boundaries, and increased resistance to intergranular corrosion cracking.     

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.     

Structure and properties of high-temperature austenitic steels for superheater tubes

The structure and properties of high-temperature austenitic steels intended for superheater tubes are analyzed. Widely used Kh18N10T (AISI 304) and Kh16N13M3 (AISI 316) steels are found not to ensure a stable austenitic structure and stable properties during long-term thermal holding under stresses. The hardening of austenitic steels by fine particles of vanadium and niobium carbides and nitrides and γ′-phase and Fe₂W and Fe₂Mo Laves phase intermetallics is considered. The role of Cr₂₃C₆ chromium carbides, the σ phase, and coarse precipitates of an M ₃B₂ phase and a boron-containing eutectic in decreasing the time to failure and the stress-rupture strength of austenitic steels is established. The mechanism of increasing the stress-rupture strength of steels by boron additions is described. The chemical compositions, mechanical properties, stress-rupture strength, and creep characteristics of Russian and foreign austenitic steels used or designed for superheater tubes intended for operation under stress conditions at temperatures above 600°C are presented. The conditions are found for increasing the strength, plasticity, and thermodeformation stability of austenite in steels intended for superheater tubes operating at 700°C under high stresses for a long time.     

Precipitation of Second Phases in High-Interstitial-Alloyed Austenitic Steel

The precipitation reaction of an austenitic stainless steel containing N + C was investigated using transmission electron microscopy. The main precipitate formed during isothermal aging at 1123 K (850 °C) was M₂₃C₆ carbide, and its morphology gradually changed in a sequence of intergranular (along grain boundary) → cellular (or discontinuous) → intragranular (within grain interior) form with aging time. Irrespective of different morphologies, the M₂₃C₆ was consistently related to austenite matrix in accordance with the cube-on-cube orientation relationship. Based on the analysis of electron diffraction, two variants of intragranular M₂₃C₆ were identified, and they were related to each other by twin relation. Prolonged aging produced other types of precipitates—the rod-shaped Cr₂N and the coarse irregular intermetallic sigma phase. The similarities and differences in precipitation behavior between N only and N + C alloyed austenitic stainless steels are briefly discussed.     

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.     

Nanoscale Cementite Precipitates and Comprehensive Strengthening Mechanism of Steel

This article summarizes the state of the art of the comprehensive strengthening mechanism of steel. By using chemical phase analysis, X-ray small-angle scattering (XSAS), room temperature organic (RTO) solution electrolysis and metal embedded sections micron-nano-meter characterization method, and high-resolution transmission electron microscopy (TEM) observation, the properties of nanoscale cementite precipitates in Ti microalloyed high-strength weathering steels produced by the thin slab continuous casting and rolling process were analyzed. Except nanoscale TiC, cementite precipitates with size less than 36 nm and high volume fraction were also found in Ti microalloyed high-strength weathering steels. The volume fraction of cementite with size less than 36 nm is 4.4 times as much as that of TiC of the same size. Cementite with high volume fraction has a stronger precipitation strengthening effect than that of nanoscale TiC, which cannot be ignored. The precipitation strengthening contributions of nanoscale precipitates of different types and sizes should be calculated, respectively, according to the mechanisms of shearing and dislocation bypass, and then be added with the contributions of solid solution strengthening and grain refinement strengthening. A formula for calculating the yield strength of low-carbon steel was proposed; the calculated yield strength considering the precipitation strengthening contributions of nanoscale precipitates and the comprehensive strengthening mechanism of steels matches the experimental results well. The calculated σ _s  = 630 to 676 MPa, while the examined σ _s  = 630 to 680 MPa. The reason that “ultrafine grain strengthening can not be directly added with dislocation strengthening or precipitation strengthening” and the influence of the phase transformation on steel strength were discussed. The applications for comprehensive strengthening theory were summarized, and several scientific questions for further study were pointed out.     

Overview no. 63 Non-equilibrium grain boundary segregation of boron in austenitic stainless steel—IV. Precipitation behaviour and distribution of elements at grain boundaries

The distribution of elements and the precipitation behaviour at grain boundaries have been studied in boron containing AISI 316L and “Mo-free AISI 316L” type austenitic stainless steels. A combination of microanalytical techniques was used to study the boundary regions after cooling at 0.29–530°C/s from 800, 1075 or 1250°C. Tetragonal M₂B, M₅B₃ and M₃B₂, all rich in Fe, Cr and Mo, precipitated in the “high B” (40 ppm) AISI 316L steel whereas orthorhombic M₂B, rich in Cr and Fe, was found in the “Mo-free steel” with 23 ppm B. In the “high B steel” a thin (<2 nm), continuous layer, containing B, Cr, Mo and Fe and having a stoichiometry of typically M₉B, formed at boundaries after cooling at intermediate cooling rates. For both types of steels a boundary zone was found, after all heat treatments, with a composition differing significantly from the bulk composition. The differences were most marked after cooling at intermediate cooling rates. In both types of steel boundary depletion of Cr and enrichment of B and C occurred. It was found that non-equilibrium grain boundary segregation of boron can affect the precipitation behaviour by making the boundary composition enter a new phase field. “Non-equilibrium phases” might also form. The synergistic effect of B and Mo on the boundary composition and precipitation behaviour, and the observed indications of C non-equilibrium segregation are discussed.     

时效处理和氮含量对316L超低碳奥氏体不锈钢冲击韧性的影响

316L超低碳不锈钢(/%:0.010～0.013C、17.50～17.67Cr、10.10～10.60Ni、1.89～2.02Mo、0.020～0.201N)由200 kg真空感应炉冶炼,并经550 mm轧机热轧成15 mm钢板。研究了1 050℃40 min水冷,750℃25～100 h空冷后316L钢的组织和冲击韧性。结果表明,随时效时间增加,316L钢的冲击功下降;同样时效时间,0.201%N的高氮316L钢的冲击功低于0.020%N较低氮316L钢,750℃100 h时效后两者的冲击功分别为40 J和150 J。低氮316L钢主要析出物为碳化物,在晶界和晶内呈细小弥散分布,尺寸为3～5μm;高氮316L钢析出物为100～200μm氮碳化物和σ-相,沿晶界分布。     

Quantitative Precipitate Classification and Grain Boundary Property Control in Co/Ni-Base Superalloys

A correlative approach is employed to simultaneously assess structure and chemistry of (carbide and boride) precipitates in a set of novel Co/Ni-base superalloys. Structure is derived from electron backscatter diffraction (EBSD) with pattern template matching, and chemistry obtained with energy dispersive X-ray spectroscopy (EDS). It is found that the principal carbide in these alloys is Mo and W rich with the M₆C structure. An M₂B boride also exhibiting Mo and W segregation is observed at B levels above approximately 0.085 at. pct. These phases are challenging to distinguish in an SEM with chemical information (EDS or backscatter Z-contrast) alone, without the structural information provided by EBSD. Only correlative chemical and structural fingerprinting is necessary and sufficient to fully define a phase. The identified phases are dissimilar to those predicted using ThermoCalc. We additionally perform an assessment of the grain boundary serratability in these alloys, and observe that significant amplitude is only obtained in the absence of pinning intergranular precipitates.

     

Nitrogen redistribution, microstructure, and elastic constant evaluation using ultrasonics in aged 316LN stainless steels

The presence of even dilute concentrations of nitrogen (0.08 mass pct) is found to have a strong influence on the microstructure of a nuclear grade 316LN austenitic stainless steel, thermally aged at 1123 K. High-resolution transmission electron microscopy (TEM) evidence of pre-precipitation reactions involving formation of Cr-N rich clusters prior to Cr₂N precipitation has been presented. A tendency for cellular precipitation has been observed on continued aging above 500 hours. Beyond 1000 hours, chi precipitates are the most frequently seen phase. The observed microstructural variations correlate well with ultrasonic velocity and attenuation measurements. The present study reveals that nitrogen in solid solution decreases all the elastic constants, namely longitudinal modulus, elastic modulus, shear modulus, and bulk modulus in this steel but has a negligible effect on Poisson’s ratio. The stages associated with the precipitation of intragranular coherent Cr₂N are, however, associated with an increase in all the elastic constants including Poisson’s ratio.     

Grain boundary segregation of an Al-Zn-Mg ternary alloy

Auger electron spectroscopy (AES) has been used to measure the grain boundary concentration profiles of alloy additions in an A1-5.5 pct Zn-2.5 pct Mg ternary in as-quenched, under-, peak-, and over-aged conditions. The AES depth profiles show marked segregation of Mg and Zn to the grain boundary, in contrast to that reported previously on similar A1 alloys. It is found that this apparent contradiction can be resolved by exploiting the plasmonloss features of the AES spectra to help elucidate the grain boundary segregation. With the AES/plasmon-loss measurements, one can determine not only the concentration of Mg and Zn at the grain boundary, but also the metallurgical environments surrounding the alloy additions. It is shown that, for over-aged specimens of the Al alloy, only a fraction of the total Mg at the grain boundary is incorporated in MgZn₂ precipitates, the remainder being segregated to within a few atomic layers of the boundary.     

Carbide precipitation,grain boundary segregation,and temper embrittlement in NiCrMoV rotor steels

This paper presents a study of carbide precipitation, grain boundary segregation, and temper embrittlement in NiCrMoV rotor steels. One of the steels was high purity, one was doped with phosphorus, one was doped with tin, and one was commercial purity. In addition, two NiCrV steels, one high purity and one doped with phosphorus, were examined. Carbide precipitation was studied with analytical electron microscopy. It was found that after one hour of tempering at 600 ‡C only M₃C carbides were precipitated in the NiCrMoV steels. These were very rich in iron. As the tempering time increased, the chromium content of the M₃C carbides increased significantly, but their size did not change. Chromium rich M₇C₃ precipitates began to form after 20 hours of tempering, and after 50 hours of tempering Mo-rich M₂C carbides were precipitated. Also, after 100 hours of tempering, the matrix formed bands rich in M₃C or M₇C₃ and M₂C particles. Tempering occurred more rapidly in the NiCrV steels. Grain boundary segregation was studied with Auger electron spectroscopy. It was found that the amount of phosphorus and tin segregation that occurred during a step-cooling heat treatment after tempering was less if a short time tempering treatment had been used. It will be proposed that this result occurs because the low temperature tempering treatments leave more carbon in the matrix. Carbon then compctes with phosphorus and tin for sites at grain boundaries. This compctition appears to affect phosphorus segregation more than tin segregation. In addition to these two impurity elements, molybdenum and nickel segregated during low temperature aging. The presence of molybdenum in the steel did not appear to affect phosphorus segregation. Finally, it will be shown that all of the steels that contain phosphorus and/or tin exhibit some degree of temper embrittlement when they are aged at 520 ‡C or are given a step-cooling heat treatment. Of the NiCrMoV steels, the phosphorus-doped steel showed the least embrittlement and the commercial purity steel the most. The phosphorus-doped NiCrV steel was also more susceptible to temper embrittlement than the phosphorus-doped NiCrMoV steel. This latter difference was attributed to molybdenum improving grain boundary cohesion. It was also found that as the segregation of phosphorus or tin to the grain boundaries increased, the measured embrittlement and the amount of intergranular fracture increased. However, there was a large amount of scatter in all of these data and the trends were only qualitative. All parts of this study are compared in detail to others in the literature, and general trends that can be discerned from all of these results are presented. Formerly with the University of Pennsylvania, Department of Materials Science, Philadelphia, PA     

Correlation of Electrochemical Noise Parameters with Degree of Sensitization in AISI Type 316LN Stainless Steel

Degree of sensitization in 316LN stainless steel (SS) specimens sensitized at 898, 923 and 948 K for 500 h was obtained using double loop electrochemical potentiokinetic reactivation (DLEPR) technique as 7.4, 14.5 and 9.3% respectively. The sensitized specimens were pulsed polarized so that only Cr-depleted regions of the sensitized grain boundaries contributed to the electrochemical noise (EN) study. The DOS values evaluated from DLEPR technique were correlated with the EN parameters viz. standard deviation of current, σ_I and characteristic charge, q and characteristic frequency, f _n , obtained from shot noise analysis in order to assess the extent of intergranular corrosion (IGC) attack in 316LN SS. The plot of σ_I versus time showed highest σ_I values for the specimen sensitized at 923 K for 500 h, indicating high grain boundary dissolution and hence, severe IGC attack, whereas the specimen sensitized at 898 K for 500 h showed the least σ_I values indicating lower dissolution and least IGC attack. 316LN SS specimen heat-treated at 948 K for 500 h showed intermediate grain boundary dissolution rate. The charge q, determined from σ_I versus time plot showed a good correlation (>99%) with the DOS values obtained from DLEPR experiments. The power spectral density values of the current signal in the frequency independent region were found to have excellent correlation with these observations. The above findings were further supported by scanning electron microscopic examination which showed an increase in grain boundary width in the sensitized specimens when the heat-treatment temperature was raised from 898 to 923 K and on further increasing the temperature to 948 K, a marginal decrease in the grain boundary width was observed.     

Precipitate Redistribution during Creep of Alloy 617

Nickel-based superalloys are being considered for applications within advanced nuclear power generation systems due to their high-temperature strength and corrosion resistance. Alloy 617, a candidate for use in heat exchangers, derives its strength from both solid solution strengthening and the precipitation of carbide particles. However, during creep, carbides that are supposed to retard grain boundary motion are found to dissolve and reprecipitate on boundaries in tension. To quantify the redistribution, we have used electron backscatter diffraction (EBSD) and energy-dispersive spectroscopy (EDS) to analyze the microstructure of 617 after creep testing at 900 °C and 1000 °C. The data were analyzed with respect to the location of the carbides (e.g., intergranular vs intragranular), grain boundary character, and precipitate type (i.e., Cr rich or Mo rich). We find that grain boundary character is the most important factor in carbide distribution; some evidence of preferential distribution to boundaries in tension is also observed at higher applied stresses. Finally, the results suggest that the observed redistribution is due to the migration of carbides to the boundaries and not the migration of boundaries to the precipitates.     

Microstructure and Precipitation Behavior in HAZ of V and Ti Microalloyed Steel

Three steels containing 0. 05%C-0. 1%V-0. 01%N (steel V-LN), 0. 05%C-0. 1%V-0. 02%N (steel V-HN), and 0. 05%C-0. 1%V-0. 02%N-0. 01%Ti (steel V-HN-Ti), which were all essentially vanadium microalloyed steels, were subjected to simulating the microstructure of a coarse grained heat affected zone (CGHAZ). The process involved reheating to 1 350 °C, rapid cooling to room temperature, and varying the welding heat input from 15 kj/cm to 54 kj/cm, including four cooling rates of t_8/5 equal to 7. 5 s, 20 s, 40 s, 100 s, and the relationship of heat input to tg/_s was calculated by Quiksim software. The microstructure and precipitation of vanadium and titanium carbon nitrides are studied. The results indicate that the microstructure consists of granular bainite and some side plate ferrite in the grain boundary when the steels are produced with the highest heat input. As the heat input decreased, numerous polygonal ferrites and grain boundary ferrites appeared, and the size apparently increased. When the steel contained high nitrogen, it was considerably easier to form martensite-austenite island, which was even worse for the toughness and other properties of the steel. For the limitation of cooling time, vanadium carbon nitrides could not precipitate sufficiently, but as titanium was added, the unmelted or precipitated TiN on cooling absorbed some fraction of nitrogen in the matrix and made more precipitate positions for the round V(C, N), and thus several useful round particles could be seen in titanium-contained steel, and most of them were around TiN. By this experiment, we can conclude that with the help of titanium, nitrogen-enhanced steel had a better prior austenite grain size, was considerably easier to precipitate, reduced free nitrogen in the matrix effectively, and provided a very effective mechanism for restriction grain growth in the HAZ.     

Thermal treatment improving creep properties of nitrogen-added Mod.9Cr-1Mo steels

Generation IV reactors are being developed to produce a reliable energy safely and with an economic benefit, because nuclear energy is being seriously considered to meet the increasing demand for a world-wide energy supply without environmental effects. Ferritic/martensitic steels are attracting attention as candidate materials for the Gen-IV reactors due to their high strength and thermal conductivity, low thermal expansion, and good resistance to corrosion. In recent years, new ferritic/martensitic steels have been developed for ultra supercritical fossil power plants through advanced technologies for steel fabrication. The microstructural stability of these materials for the pressure vessel, cladding and core structure of the VHTR and SFR is very important. Nitrogen is a precipitation hardening element, and the thermal stability of nitrides is superior to that of carbides. So the formation of nitrides may improve the thermal stability of the microstructure and eventually increase the creep rupture strength of high Cr steels. The effect of nitrogen on the creep rupture strength and microstructure evolution of nitrogen-added Mod.9Cr-1Mo steels has been studied. Creep testing was carried out at 873 and 923 K under constant load conditions. The optimum controlled Cr₂X precipitates were developed by special heat treatment, and they were not dissolved after a creep deformation. These fine and stable Cr₂X precipitates contributed to the increase of the creep rupture strength. The prior austenite grain size and martensite lath width were decreased by the resultant stable nitrides.     

Precipitation Kinetics of Cr2N in High Nitrogen Austenitic Stainless Steel

The precipitation behavior of Cr2 N during isothermal aging in the temperature range from 700 ℃ to 950 ℃ in Fe-18Cr-12Mn-0.48N （in mass percent） high nitrogen austenitic stainless steel, including morphology and content of precipitate, was investigated using optical microscopy, scanning electron microscopy, and transmission electron microscopy. The isothermal precipitation kinetics curve of Cr2 N and the corresponding precipitation activation energy were obtained. The results show that Cr2N phase precipitates in a cellular way and its morphology is transformed from initial granular precipitates to lamellar ones in the cell with increasing aging time. The nose temperature of Cr2 N precipitation is about 800 ℃, with a corresponding incubation period of 30 min, and the ceiling temperature of Cr2N precipitation is 950℃. The diffusionactivation energy of Cr2 N precipitation is 296 kJ/mol.