Reversible temper embrittlement of rotor steels

The susceptibility to temper embrittlement of eight different rotor steels has been studied in terms of the effects of composition, of cooling rate from tempering temperature, of isothermal aging, of steel-making practice and of strength level and tempering temperature. The Ni Cr Mo V steels tested showed increasing susceptibility to temper embrittlement with increasing nickel content. The normally marked susceptibility of a high phosphorus 3 pct Cr Mo steel was eliminated by the removal of manganese. Embrittlement in a 3 pct Ni Cr Mo V steel was caused by the equilibrium segregation of solute atoms to the prior austenite grain boundaries. Two Cr Mo V steels tested were not susceptible to temper embrittlement. Electroslag remelting and refining had very little effect on the susceptibility of the steels tested. Strength level and tempering temperature had no effect on the degree of embrittlement of the 3 pct Ni Cr Mo V disc steel. The possibilities of remedial action include an adjustment of the post tempering cooling rate, to optimize the conflicting interests of minimum temper embrittlement and adequate stress relief, and the production of very low manganese rotor steels.     

The effects of composition and carbide precipitation on temper embrittlement of 2.25 Cr-1 Mo steel: Part I. Effects of P and Sn

Temper embrittlement of 2.25 Cr-1 Mo steel doped with P and Sn was studied systematically. Carbide extraction by electrolysis, X-ray diffraction, transmission (replica) electron microscopy, chemical analysis of the matrix, and scanning Auger microprobe analysis were conducted to determine the effect of carbide precipitation and subsequent variation of the Mo concentration in solution on the segregation of P. These analyses were correlated with the ductile-to-brittle transition temperature (measured by use of a slow-bend test), as well as hardness measurements and fractographic information obtained by scanning electron microscopy. The results indicate that the principal role of Mo is to suppress embrittlement by scavenging of P, presumably by a Mo-P compound formation, thereby diminishing P segregation. However, due to the stronger interaction between Mo and C, Mo is precipitated in an M₂C carbide during tempering or aging, and the matrix is depleted of Mo. The P thereby released segregates at a rate consistent with the rate of M₂C precipitation. At a Mo concentration >0.7 pct the beneficial effect of Mo is decreased due to enhanced M₂C precipitation, the content of Mo in solution remaining essentially constant. The M₂C is formed at the expense of Cr-rich M₇C₃; this results in more Cr in solution, thereby permitting more Cr-P cosegregation, and embrittlement increases. Tin was found not to produce temper embrittlement in this steel when present at concentrations up to 0.04 pct.     

Effect of cerium on temper embrittlement of P-doped Mn structural steels

The effect of cerium on temper embrittlement of P-doped Mn structural steels has been investigated by measurements of the ductile-brittle transition temperature and observations by AES, SIMS and SEM of the fracture surfaces of isothermally embrittled steels. It is shown that P can bring about the temper embrittlement of Mn structural steels; cerium may reduce the temper embrittlement of the steels and the segregation of cerium to grain boundaries may play an important part in reducing the temper embrittlement of the steels.     

Mechanism of Embrittlement and De-Embrittlement for 2.25Cr-1Mo Steel

 The constant embrittlement curve for constant segregation concentration on grain boundary of impurity element P and relationship between equilibrium grain boundary segregation concentration and operation time for 225Cr-1Mo steel were derived based on the theory of equilibrium grain boundary segregation. The mechanism of step-cooling test and mechanism of de-embrittlement for 225Cr-1Mo steel were explained. The segregation rate will increase but equilibrium grain boundary segregation concentration of impurity element P will decrease as temperature increases in the range of temper embrittlement temperature. There is one critical temperature of embrittlement corresponding to each embrittlement degree. When the further heat treating temperature is higher than critical temperature, the heat treating will become a de-embrittlement process; otherwise, it will be an embrittlement process. The critical temperature of embrittlement will shift to the direction of low temperature as further embrittlement. As a result, some stages of step-cooling test would change into a de-embrittlement process. The grain boundary desegregation function of impurity element P was deduced based on the theory of element diffusion, and the theoretical calculation and experimental results show that the further embrittlement or de-embrittlement mechanism can be interpreted qualitatively and quantitatively by combining the theory of equilibrium grain boundary segregation with constant embrittlement curve.     

The effect of titanium on phosphorus solubility in a Ni-Cr steel from a study of free-surface segregation

The rate of phosphorus segregation to the free surface of a low carbon Ni-Cr steel con-taining 0.06 wt pct P was found to be severely retarded at 833 K by the addition of 0.3 wt pct titanium to the alloy. The results indicate that the reported elimination of temper embrittlement in a phosphorus doped low carbon Ni-Cr steel, by a titanium addition, is due to inhibition of phosphorus segregation to grain boundaries because of removal of phosphorus from solid solution. An analysis of the segregation kinetics led to the con-clusion that the titanium addition lowered the concentration of phosphorus in solution to 0.012 ± 0.002 wt pct at 833 K. This was confirmed by experiments on a titanium-free al-loy containing 0.015 ± 0.0015 wt pct phosphorus.     

Temper embrittlement of Ni-Cr Steels by phosphorus

Temper embrittlement in 3.5 pct Ni, 1.7 pct Cr steels doped with P and isothermally aged at several temperatures was studied by measurements of ductile-to-brittle transition temperature and hardness, which were correlated with observations of the intergranular fracture surfaces by Auger electron spectroscopy and scanning electron fractography. It is shown that if all other factors remain constant, the effect of a small change in the matrix hardness can be very large; “overaging” (a maximum in embrittlement with respect to aging time) was found to result from softening rather than from a reversal of segregation of P. Nickel was found to be segregated at the grain boundaries, and both Ni and Cr appear to enhance the amount of segregated P. The major role of Cr was found to be its effect of increasing matrix hardness (by enhancing hardenability and resistance to softening during tempering), resulting in an increased susceptibility to temper embrittlement. The effect of variations in the roughness of grain boundary topography appears to be small. It is shown that the segregation of P to grain boundaries can be accounted for by diffusion from the matrix and is consistent with the hypothesis of equilibrium (Gibbsian) segregation. The results are in qualitative agreement with the thermo-dynamic theory of Guttmann. Formerly a Research Fellow at the Department of Materials Science, University of Pennsylvania, Philadelphia, PA 19174.     

The thermodynamics of interactive co-segregation of phosphorus and alloying elements in iron and temper-brittle steels

The thermodynamics of co-segregation and precipitation of P and alloying elements (transition metals M and carbon) involved in temper embrittlement of steels are studied quantitatively on the basis of the regular solution model for co-segregation. The equations of this model are fitted to the available Auger data for grain boundary segregation in high purity iron-base alloys and commercial steels, allowing the determination of the intrinsic segregation energies ΔG_i ^o and of the binary β_P ^gb, β_c ^gb and ternary β_PC ^gb, ß_MP ^gb interaction coefficients in the grain boundaries. This analysis shows that Ni, Cr, and Mo do not segregateper se in iron whereas Mn does weakly, and that the segregation of these elements is essentially driven by that of P through the strongβ_MP ^gb attractive interaction energyat the boundaries. This energy, which increases in the order Ni, Mn, Cr, Mo, is remarkably close to the bulk values β_MP ^B in the corresponding phosphides as calculated on the basis of solubility data. The scavenging of P by M elements with largebulk M-P interactions is shown to play a determining role in low Mo and high (12 pct) Cr steels. The beneficial role of carbon is complex since it drives Mo to the grain boundaries due to the large Mo-C attraction, but it also strongly opposes P segregation due to the large repulsive P-C interaction.     

Carbide Evolution in Temper Embrittled NiCrMoV Bainitic Steel

Phosphorus segregation to prior austenite grain boundaries in low alloy steel from exposure to temperatures of 300 to 600°C results in a susceptibility for intergranular fracture referred to as “temper embrittlement”. It has been observed that alloying steel with Mo greatly reduces the phosphorus segregation kinetics. Therefore changes in the ferrite matrix composition from carbide precipitation and evolution involving Mo can influence the segregation phenomenon and fracture properties. This study uses analytical electron microscopy of extraction replicas to characterize the changes in carbide chemistry of a NiCrMoV bainitic steel with 0.25 wt% C that accompany the phosphorus segregation during aging at 480°C for up to 3400 hr. The steel was doped with 0.02 wt% P and tempered at 650°C to two different hardness levels, i.e., two different initial carbide distributions. The amount of grain boundary phosphorus segregation produced by aging at 480°C correlates with the level of molybdenum that remains in solution in the ferritic matrix whereas changes in vanadium and chromium appear to have less influence on the temper embrittlement.     

合金元素对Cr-Mo钢第二类回火脆性影响研究综述

对于一些长期在中温条件下服役的Cr-Mo钢(2.25Cr1Mo),由于钢中P、S等有害杂质元素在服役过程中不断向晶界偏聚,降低了晶界结合力,致使该类钢出现第二类回火脆性这一关键问题.为了探寻降低这类Cr-Mo钢第二类回火脆性倾向的有效方法,提高材料安全服役可靠性,从溶质元素偏聚机制出发,总结分析了合金元素晶界偏聚及改善...     

Effects of Mn,Si, and purity on the design of 3.5NiCrMoV, 1CrMoV,and 2.25Cr-1Mo bainitic alloy steels

Three high-temperature bainitic alloy steels were evaluated in the laboratory to determine the effects of Mn, Si, and impurities (i.e., S, P, Sn, As, and Sb) on microstructure and mechanical properties. The alloy steels were 3.5NiCrMoV and CrMoV, which are used for turbine rotors, and 2.25Cr-1Mo, which is used in pressure vessel applications. The important effects of Mn, Si, and impurities, which should control the design of these high-temperature bainitic steels, are presented. Key results are used to illustrate the influence of these variables on cleanliness, overheating, austenitizing, hardenability, tempering, ductility, toughness, temper embrittlement, creep rupture, and low-cycle fatigue. Low levels of Mn, Si, and impurities not only result in improved temper embrittlement resistance in these steels but also lead to an improvement in creep rupture properties (i.e., improved strength and ductility). These results have produced some general guidelines for the design of high-temperature bainitic steels. Examples illustrating the implementation of the results and the effectiveness of the design guidelines are provided. Largely based on the benefits shown by this work, a high-purity 3.5NiCrMoV steel, which is essentially free of Mn, Si, and impurities, has been developed and is already being used commercially. T. OHHASHI was formerly Research Scientist, Japan Steel Works, Ltd., Muroran Research Laboratory, 4 Chatsumachi, Muroran, 051 Japan.     

Grain boundary composition and associated hydrogen cracking of modified 4130 steels

Earlier work on AISI 4130 steels showed that phosphorus segregation to prior austenite grain boundaries was the primary cause for intergranular fracture of these steels when exposed to hydrogen. Reduction of P segregation to grain boundaries by removing the strong segregation couples of Mn-P and Si-P was expected to increase the hydrogen stress cracking resistance of 4130 type steels. Elimination of Mn and/or Si did reduce the concentration of P at prior austenite grain boundaries, but allowed segregation of S and N which acted in the same manner as P, promoting intergranular hydrogen stress cracking.     

Temper embrittlement of Ni-Cr steel by antimony:II. Effects of addition of titanium

It is shown that the addition of 0.1 pct Ti to a low carbon Ni-Cr steel can eliminate most of the susceptibility to temper embrittlement due to both step cooling and isothermal aging. The mechanism by which Ti acts is complex and not yet clear. It suppresses carbide formation during the embrittlement heat treatment, which should retard the rate of embrittlement (cf. Part I). However, it also appears to interact with Ni and Sb by enhancing the segregation of Ni to grain boundaries and by mitigating the embrittling effect of Sb.     

The influence of Mo on P-lnduced temper embrittlement in Ni-Cr steel

The effects of the addition of Mo on the temper embrittlement susceptibility of a P-doped Ni-Cr steel were studied. It is shown that P-induced temper embrittlement can be eliminated for aging times up to 1000 h at 475 and 500°C, presumably by the scavenging effect of Mo on P, if the Mo : P ratio is high enough and if the Mo is not precipitated by C. The latter reaction, which allows temper embrittlement to proceed, can occur more rapidly as the aging temperature or C content is raised. Formerly Research Fellow in the Department of Metallurgy and Materials Science, University of Pennsylvania H. C. Feng Formerly with Research Staff, LRSM, University of Pennsylvania     

Temper embrittlement of Ni-Cr steel by antimony:II. Effects of addition of titanium

It is shown that the addition of 0.1 pct Ti to a low carbon Ni-Cr steel can eliminate most of the susceptibility to temper embrittlement due to both step cooling and isothermal aging. The mechanism by which Ti acts is complex and not yet clear. It suppresses carbide formation during the embrittlement heat treatment, which should retard the rate of embrittlement (cf. Part I). However, it also appears to interact with Ni and Sb by enhancing the segregation of Ni to grain boundaries and by mitigating the embrittling effect of Sb. Formerly a Post-Doctoral Fellow.     

Clean steels for steam turbine rotors—their stress corrosion cracking resistance

This work presents the results of a comprehensive study concerning stress corrosion crack growth rates in steam turbine rotor steels exposed to hot water. The effects of stress intensity, temperature, and dissolved gases in the water have been investigated. Special attention has been given to the influence of impurities and alloying elements in the steel such as P, S, Mn, Si, Mo, and Ni, and to the effect of yield strength and fracture toughness on the growth rates of stress corrosion cracks. The results of this study clearly show that there exists a threshold stress intensity of about 20 MNm^−3/2 above which the invariably intergranular stress corrosion cracks grow at a constant, stress-independent velocity. This plateau stress corrosion crack growth rate isnot affected by the oxygen and carbon dioxide concentration in the water. The temperature and the yield strength of the steel have a strong influence on the growth rate of stress corrosion cracks. In contrast, there isno effect of the steel composition within the range investigated, neither of the impurity elements such as P and S, nor of the major alloying elements such as Mn, Si, Mo, and Ni. Steels with low fracture toughness due to temper embrittlement do not exhibit faster stress corrosion crack growth rates in water than nonembrittled steels. No direct relationship between intergranular temper embrittlement and intergranular stress corrosion crack growth in water can be demonstrated.     

Effects of Thermal History and Microstructure on Segregation of Phosphorus and Alloying Elements in the Heat-Affected Zone of a Low Alloy Steel

The grain boundary segregation of phosphorus and alloying elements in the heat-affected zone (HAZ) of a low alloy steel was studied quantitatively with atom probe tomography. Non-equilibrium segregation mainly occurred during welding and subsequent fast cooling, leading to remarkable segregation of P, C, Mn, and Mo. The segregation of these four types of solutes showed similar microstructure-dependence at this stage, in which the segregation levels are higher in coarse-grained HAZ and intercritically reheated coarse-grained HAZ than in fine-grained HAZ. After simulated aging, P and Mn showed further enrichment at grain boundaries through equilibrium segregation, while desegregation was observed for C and Mo. In addition, it seems that precipitation of Mo at dislocations was greatly promoted during aging, which probably also contributed to the increase of P and Mn at grain boundaries.     

The use of a boron addition to prevent intergranular embrittlement in Fe-12Mn

Fe-12 Mn alloys undergo failure by catastrophic intergranular fracture when tested at low temperature in the as-austenitized condition, a consideration which prevents their use for structural applications at cryogenic temperatures. The present research was undertaken to identify modifications in alloy composition or heat treatment which would suppress this embrittlement. Chemical and microstructural analyses were made on the prior austenite grain boundaries within the alloy in its embrittled state. These studies failed to reveal a chemical or microstructural source for the brittleness, suggesting that intergranular brittleness is inherent to the alloy in the as-austenitized condition. The addition of 0.002 to 0.01 wt pct boron successfully prevented intergranular fracture, leading to a spectacular improvement in the low temperature impact toughness of the alloy. Autoradiographic studies suggest that boron segregates to the austenite grain boundaries during annealing at temperatures near 1000 °C. The cryogenic toughness of a Fe-12Mn-0.002B alloy could be further improved by suitable tempering treatments. However, the alloy embrittled if inappropriate tempering temperatures were used. This temper embrittlement was concom-itant with the dissolution of boron from the prior austenite grain boundaries, which reestablishes the intergranular fracture mode.     

Influence of impurity segregation on temper em brittlement and on slow fatigue crack growth and threshold behavior in 300-M high strength steel

Interactions between hydrogen embrittlement and temper embrittlement have been examined in a study of fracture and low growth rate (near-threshold) fatigue crack propagation in 300-M high strength steel, tested in humid air. The steel was investigated in an unembrittled condition (oil quenched after tempering at 650°C) and temper embrittled condition (step-cooled after tempering at 650°C). Step-cooling resulted in a severe loss of toughness (approximately 50 pct reduction), without loss in strength, concurrent with a change in fracture mode from micr ovoid coalescence to inter granular. Using Auger spectroscopy analysis, the embrittlement was attributed to the cosegregation of alloying elements (Ni and Mn) and impurity elements (P and Si) to prior austenite grain boundaries. Prior temper embrittlement gave rise to a substantial reduction in resistance to fatigue crack propagation, particularly at lower stress intensities approaching the threshold for crack growth(x0394;K _o). At intermediate growth rates (10^-5 to 10^-3 mmJcycle), propagation rates in both unembrittled and embrittled material were largely similar, and only weakly dependent on the load ratio, consistent with the striation mechanism of growth observed. At near-threshold growth rates (<10⁻⁵ to 10⁻⁶ mmJcycle), embrittled material exhibited significantly higher growth rates, 30 pct reduction in threshold ΔK_o values and intergranular facets on fatigue fracture surfaces. Near-threshold propagation rates (and ΔK_o values) were also found to be strongly dependent on the load ratio. The results are discussed in terms of the combined influence of segregated impurity atoms (temper embrittlement) and hydrogen atoms, evolved from crack tip surface reactions with water vapor in the moist air environment (hydrogen embrittlement). The significance of crack closure concepts on this model is briefly described. ntmis]formerly with the Lawrence Berkeley Laboratory, University of California in Berkeley. Formerly with the Lawrence Berkeley Laboratery, University of California in Berkeley.     

Effects of compositional variations and aging treatments on the fracture behavior of H Y130 steel in air and hydrogen

The effects of variations in the bulk concentrations of Mn, Si, and Al on the fracture behavior of HY 130 steel were studied by means of Charpy tests, measurements of brittle fracture stress at 77 K, fracture toughness tests, and measurements of the threshold stress intensity for crack extension (K_TH) in H₂. The main focus was on temper embrittlement and hydrogen-induced cracking (HIC). The susceptibility to intergranular HIC was characterized by the K_TH and was directly related to the susceptibility to temper embrittlement. Both phenomena can be eliminated by limiting the Mn and Si contents of the steel and by avoiding contamination of the steel by Sn. The effect of Al is to cause a small age-hardening reaction, which can noticeably affect the tendency toward cleavage fracture, and to block part of the temper embrittlement reaction. Formerly Research Fellow, Department of Materials Science and Engineering, University of Pennsylvania.     

Evaluation of the effects of segregation on austenite grain boundary energy in Fe-C-X alloys

A scanning Auger microprobe study has been made of the segregation of substitutional alloying elements to austenite grain boundaries in Fe-C-X alloys (where X = Mn, Ni, Si, Co, and Mo). The grain boundary enrichments in X are considerably smaller than those previously estimated from the thermal grooving method but appear consistent with other SAM results in the literature. Mo exhibits the highest enrichment factor, those for Si and Mn are intermediate, and no appreciable grain boundary enrichment of either Co or Ni is observed. In view of the special relevance of this information to nucleation kinetics of austenite decomposition products at austenite grain boundaries, the reductions in grain boundary energy attending the measured enrichments are evaluated using the model of interactive segregation of interstitial and substitutional solutes formulated by Guttmann and McLean. These calculations were performed under two different (limiting) conditions: (i) equilibrium segregation of both solutes is fully achieved at the isothermal reaction temperatures, and (ii) the boundary concentration of X is fully inherited from the austenitizing temperature and only paraequilibrium segregation of carbon is achieved. Various characteristics of interactive segregation are also discussed in terms of the interaction and binding energies of each solute. Formerly a Graduate Student, Department of Metallurgical Engineering and Materials Science, Carnegie Mellon University, Pittsburgh, PA15213 Formerly with Oak Ridge National Laboratory, Oak Ridge, TN 37830