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.     

Resistance of Trip 800 Steels in a Sour Environment Containing H2S

We have evaluated the resistance of two samples of TRIP 800 steel prepared under laboratory conditions at the Faculty of Metallurgy and Materials Engineering (FMME) V?B (Technical University of Ostrava, Czech Republic) in a sour environment containing H₂S. The first steel investigated had a C–Mn–Si composition, and the second steel had a C–Mn–Si–Al composition. Both TRIP steels were characterized using the yield strength in the range 420 to 450 MPa and tensile strength in the range 880 to 900 MPa. The TRIP steel samples were in the form of sheets with a thickness of 1.5 mm. The residual austenite content was 11% and 13%, respectively, in the two steels studied. The resistance to hydrogen embrittlement was evaluated in a sour environment that contained hydrogen sulphide using hydrogen‐induced cracking (HIC) and sulphide stress cracking (SSC) tests performed in accordance with NACE standards. Both TRIP 800 steels showed a high resistance to hydrogen embrittlement, and no SSC cracks were observed. Some cracking arising from HIC was observed in both steels. The measured parameters showed some variation; in some cases they were lower than recommended limits, but in other cases the measured parameters were higher (e.g., the crack length ratio was up to 70%). The cracks initiated preferentially at non‐metallic inclusions, either at elongated manganese sulphide particles, or at oxide stringers that were rich in Al.     

Effects of chromium on the temper embrittlement and wear resistance of 0.25% C low-alloy cast steel

The effects of additions of 0.6 to 2.0% Cr on the temper embrittlement behaviour of 0.25 C–1.0 Si–1.3 Mn cast steel under several hardening conditions were studied. The susceptibility to temper embrittlement, transgranular and intergranular fracture were increased as the chromium content increased when the steels were tempered at 350°C and slowly cooled from 550°C. The impact toughness and abrasion resistance of the steels were found to depend to a great extent on the Cr-content and tempering temperature.     

The effect of impurities and strength level on hydrogen induced cracking in a low alloy turbine steel

The effect of impurities on the threshold stress intensity for cracking in H₂S (K{ISCC}) has been investigated at various yield strength levels for a low alloy steel. Results show that the effect of impurities on K_ISCC is a function of the yield strength level. At low yield strength levels the K_ISCC of the steel is lowered markedly due to additions of impurities. However, at higher yield strength levels the K_ISCC data for pure and impure steels converge to a single value. In addition, the effect of yield strength level on Xiscc is a function of the degree of temper embrittlement caused by impurity segregation. For small degrees of temper embrittlement, increasing the yield strength decreases the -Kiscc appreciably, while for large degrees of temper embrittlement,K _ISCC is relatively insensitive to the yield strength. At K_ISCCvalues below about 50 MPa Vm, the percentage of intergranular fracture in H₂S is found to be uniquely related to K_ISCC regardless of the yield strength-impurity combination by which a givenK _ISCC is obtained. Results of the study indicate that the K_ISCC OF steels is affected by impurities, yield strength and H2S both directly and indirectly via interactive mechanisms.     

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.     

Internal hydrogen embrittlement of ultrahigh-strength AERMET 100 steel

Near-peak-aged AERMET 100 is susceptible to severe internal hydrogen embrittlement (IHE) at 23 °C, if a sufficient diffusible hydrogen content is present, compromising the high toughness of this ultrahigh-strength steel (UHSS). Evidence includes the threshold stress intensity for subcritical IHE (K _TH ) as low as 10 pct of the plane-strain fracture toughness (K _IC ) and a fracture-mode transition from microvoid coalescence to brittle transgranular (TG) cracking, apparently along martensite lath interfaces and cleavage planes. The K _TH value decreases from a K _IC value of 132 to 143 MPa√m to 12 MPa√m, and the amount of brittle TG fracture increases to nearly 100 pct as the concentration of diffusible H increases from essentially 0 to 8 wppm, with severe embrittlement in the 0 to 2 wppm H regime. The IHE is time dependent, as evidenced by increasing K _TH values with increasing dK/dt and K-independent subcritical crack growth rates, and is attributed to diffusional H repartition from reversible trap sites to the stressed crack tip. The partition distance is ∼1 μm, consistent with the fine-scale microstructure of AERMET 100. The causes of the susceptibility of AERMET 100 to TG IHE are very high crack-tip stresses and a reservoir of mobile H trapped reversibly at (Fe,Cr,Mo)₂C precipitates. These factors enable repartition of H to misoriented martensite lath interfaces and interstitial sites near cleavage planes, with each prone to decohesion along a connected path. Predissolved H also reduces the ductile fracture toughness of AERMET 100 at high loading rates, perhaps due to reduced void growth caused by H trapped strongly at undissolved metal carbides.     

The threshold stress intensity for hydrogen-induced crack growth

The crack growth rates and threshold stress intensities,K _TH, for a 3 1/2 NiCrMoV steel (0.2 pct proof stress 1200 MPa) have been measured in a hydrogen environment at various temperatures and hydrogen pressures. Fractographic evidence and the observation of alternating fast and slow crack growth nearK _TH suggests that the crack advances by the repeated nucleation of microcracks at microstructural features ahead of the main crack. Transient crack growth is observed following load increases just belowK _TH. Using the idea, from unstable cleavage fracture theory, that for fracture a critical stress must be exceeded over a critical distance ahead of the crack, and assuming that this critical stress is reduced in proportion to the local hydrogen concentration (in equilibrium with the external hydrogen atK _TH), a theoretical dependence ofK _TH on hydrogen pressure is derived which compares well with the experimental evidence.     

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.     

The effects of composition and carbide precipitation on temper embrittlement of 2.25 Cr-1 Mo steel: Part II. Effects of Mn and Si

The effects of additions of 0.7 pct Mn and/or 0.6 pct Si on the temper embrittlement behavior of 2.25 Cr-1 Mo steel at several hardness levels were determined. As in Part I, the tendency for the P segregation was dependent upon the Mo concentration in the ferrite, which is controlled by the types of carbides formed during heat treatment or aging. Additions of either Mn or Si increase the fraction of grain boundaries which adsorb P (although they do not increase the P concentration on the embrittled boundaries significantly) thereby raising the amount of temper embrittlement as measured by the transition temperature shift. Mn and Si appear to act independently and their effects appear to be additive; this is rationalized in terms of their expected influences on the segregation free energy for P in Fe.     

Hydrogen-induced delayed fracture under mode II loading

Hydrogen induced cracking (HIC) and stress corrosion cracking (SCC) of a high-strength steel 34CrNi₃Mo (T.S = 1700 MPa) under Mode II loading were investigated using notched specimens. The stress field around the notch tip was analyzed by means of finite element method. The result shows HIC and SCC under Mode II loading initiated at the back of the notch tip,i.e., θ = -110 deg, where hydrostatic stress has maximum value. However, cracking is oriented along the shear stress direction at the site, not normal to the direction of maximum principal stress component. On the contrary, if the specimens are loaded to fracture in air under Mode II loading, cracking at the maximum shear stress site around the notch tip and the cracking direction coincide with the direction of the maximum shear stress. The above facts indicate that hydrogen induced delayed plastic deformation is a necessary condition for HIC, and the nature of SCC for high-strength steel in 3.5 pct NaCl solution is HIC. The results show that HIC and SCC under Mode II loading can occur during dynamic charging with hydrogen and in 3.5 pct NaCl solution, respectively. The normalized threshold stress intensity factors under Mode II loading during dynamic charging in 1 N H₂SO₄ + 0.25 g As₂O₃/L solution and in 3.5 pct NaCl solution are K_IIH/K_IIX = 0.1 and K_IISCC/K_IIX = 0.45, respectively. The corresponding values under Mode I loading are K_IH/K_IX = 0.02 and K_ISCC/K_IX = 0.37, where K_IIX and K,_IX are critical values loaded to failure in air under Mode II and Mode I loading, respectively. Thus, (K_IIH/K_IIX)/ K_IH/K_IX) = 5 and (K_IISCC/K_IIX)/K,(_ISCC/K_IX) = 1.2. A typical intergranular fracture was observed during HIC and SCC under Modes II and I loading. But the fracture surfaces of specimens failed in air are composed of dimples for both kinds of loading. Formerly Student at Beijing University of Iron and Steel Technology     

特厚临氢设备用钢12Cr2Mo1R(SA387Gr.22Cl.2)的试制简

 介绍了特厚临氢设备用12Cr2Mo1R(HIC)钢板的生产工艺和技术指标,详细研究了钢板热处理工艺与组织对模拟焊后热处理和回火脆化倾向等性能的关系。以118mm厚钢板为例,给出了化学成分及力学性能结果,结果表明该特厚临氢设备用12Cr2Mo1R钢板成分均匀、杂质元素含量低、综合力学性能优良、回火脆化敏感性低。     

0Cr17Ni钢回火脆性机理分析

 对淬火后不同温度回火的0Cr17Ni不锈钢进行了冲击试验,发现该材料存在较严重的回火脆性。通过透射电镜（TEM）、扫描电镜（SEM）、X射线衍射仪（XRD）和俄歇电子谱仪（AES）的观察分析,研究了0Cr17Ni不锈钢产生回火脆性的原因。结果表明：该材料发生高温回火脆性的断裂属于解理与准解理复合型断裂,而并非是典型的沿晶断裂,导致回火脆性断裂的主要原因是回火过程中出现的针状碳化物。     

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.     

Stress corrosion cracking in high strength steel under mode III loading

Stress corrosion cracking (SCC) of high-strength steel in aqueous environment and hydrogen induced cracking (HIC) during dynamic charging under Mode III loading were investigated. The threshold stress intensities for SCC and HIC under Modes III and I were measured and compared. It was found that both SCC and HIC under Mode III loading initiated and propagated on the planes inclined at 45 deg to the notch plane, differing from that under Mode I loading. The fracture surfaces, however, revealed intergranular facets, similar to that under Mode I loading. The addition of thiourea decreased the threshold value for SCC under Mode III and Mode I loading, which was still higher than that for dynamic charging. The threshold values of both SCC and HIC under Mode III were larger than that under Mode I,i.e., K_IIIH> K_IH, K_IIISCC > K_ISCC. Based upon the fracture mechanics analysis, this difference is attributed to the different equilibrium hydrogen concentration between Modes III and I loading. These results give strong evidence that the SCC mechanism in high strength steel under Mode III loading is also related to hydrogen induced cracking. Formerly Student at Beijing University of Iron and Steel     

Effect of microstructure on the temper embrittlement of Cr-Mo-V steels

The effect of transformation product on the temper embrittlement susceptibility of a Cr-Mo-V steel doped with P and Sn has been investigated at different strength levels. Results show that at low strength levels (< 10R _C ) embrittlement susceptibilities of tempered bainite and ferrite-pearlite structures are comparable to each other, but lower relative to tempered martensite. The lower susceptibility of tempered bainite relative to tempered martensite obtains up to about 40R _C , above which the susceptibilities for the two structures are similar. Variation of embrittlement susceptibility with microstructure is completely consistent with the degree of grain boundary segregation of P and Sn. The segregation is smaller in bainite than in martensite at a given strength level and increases with increasing strength level for a given structure. When compared at the same degree of embrittlement (i.e., same shift in FATT), the amount of grain boundary segregate and the extent of intergranular fracture are lower in tempered bainite compared to martensite indicating that embrittlement of interfaces other than prior austenite boundaries might be an important factor in the embrittlement of bainite structures.     

The effect of tempering temperature on near- threshold fatigue crack behavior in quenched and tempered 4140 steel

Fatigue crack growth in compact tension samples of high purity 4140 steel quenched and tempered to various strength levels was investigated. Tempering temperatures of 200, 400, 550, and 700 °C produced yield strengths from 1600 to 875 MPa, respectively. Crack propagation and crack closure were monitored inK-decreasing tests performed underR = 0.05 loading conditions in laboratory air. Results indicated that as the yield strength increased the crack growth rate increased at a given ΔK and ΔK_th decreased. Threshold values varied from 2.8 MPa m^1/2 (200 °C temper) to 9.5 MPa m_1/2 (700 °C temper). Cracks in the 200 °C tempered samples grew by an intergranular mechanism following prior austenite grain boundaries probably caused by hydrogen embrittlement or tempered martensite embrittlement. Tempering above 200 °C produced transgranular fatigue crack growth. The level of crack closure increased with tempering temperature and with crack propagation in a given tempered condition. Crack closure was caused by a combination of plasticity-induced and oxide-induced mechanisms. The use of an effective stress intensity range based on crack closure consolidated the fatigue crack growth curves and the threshold values for all tempering temperatures except 200 °C. Formerly Graduate Research Assistant, Department of Materials Science and Engineering, Stanford University, Stanford, CA. Formerly Professor, Department of Materials Science and Engineering, Stanford University, Stanford, CA.     

Fe?Mn?(Al)?C高强韧性钢氢脆微观机制的研究进展

随着汽车行业的快速发展,轻量化汽车用钢的研发和应用越来越广泛。抗拉强度超过1000 MPa的第二、三代汽车用钢往往是复相组织,通过固溶、析出、变形、细晶强化等各种强化方式,在基体中形成大量缺陷,导致钢材服役过程中对氢更加敏感,容易在很小的氢溶解条件下发生氢脆。Fe?Mn?C系、Fe?Mn?Al?C系等含Mn量高的汽车结构用钢因层错能较高,不仅直接决定了其强韧性机制,还对其服役性能有重要影响。在Fe?Mn?C系TWIP钢的成分基础上,添加少量Al元素,形成Fe?Mn?(Al)?C钢,不仅能降低钢材密度,提高钢材的强韧性,也因Al元素改变了钢材的微观组织构成,一定程度上令氢脆得到缓解。但当Al含量较高时,形成低密度钢,其组织构成更加复杂,析出物更多,导致氢脆敏感性更显著。本文从Fe?Mn?(Al)?C高强韧性钢的组织构成、第二相、晶体缺陷等特征出发,综述了H在Fe?Mn?(Al)?C钢中的渗透、溶解和扩散行为,H与基体组织、析出相、晶格缺陷的交互作用,H在钢中的作用模型、氢脆机制、氢脆评价手段和方法等。并评述了Fe?Mn?(Al)?C高强韧性钢氢脆问题开展的相关研究工作和最新发展动态,指出通过第一性原理计算、分子动力学模拟和借助氢原子微印技术、三维原子探针等物理实验相结合的方法是从微观层面揭示高强韧性钢氢脆机制的未来发展方向。      

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.     

A critical evaluation of the stress-corrosion cracking mechanism in high-strength aluminum alloys

Attempts have been made to elucidate the mechanism of stress-corrosion cracking (SCC) in high-strength Al-Zn-Mg and Al-Li-Zr alloys exposed to aqueous environments by considering the temperature dependence of SCC susceptibility based upon the anodic dissolution and hydrogen embrittlement models. A quantitative correlation which involves the change of threshold stress intensity,K _ISCC, with temperature on the basis of anodic dissolution has been developed with the aid of linear elastic fracture mechanics. From the derived correlation, it is concluded that the threshold stress intensity decreases as the test temperature increases. This suggestion is inconsistent with that predicted on the basis of hydrogen embrittlement. It is experimentally observed from the Al-Zn-Mg and Al-Li-Zr alloys that the threshold stress intensity,K,_ISCC, decreases and the crack propagation rate,da/dt, over the stress intensity increases with increasing test temperature. From considering the change in SCC susceptibility with temperature, it is suggested that a gradual transition in the mechanism for the stress-corrosion crack propagation occurs from anodic dissolution in stage I, where the crack propagation rate increases sharply with stress intensity, to hydrogen embrittlement in stage II, where the crack propagation rate is independent of stress intensity.     

Effects of zinc coatings on the stress corrosion cracking and hydrogen embrittlement of low-alloy steel

The effects of electroplated and hot-dip zinc coatings on the fracture of low-alloy steel AISI 4140 bars tempered to hardnesses in the range Rc 33 to 49 were studied. Either electroplated or hot-dip zinc coatings decrease resistance to stress corrosion cracking,i.e., they reduceK _sc, the threshold stress intensity for stress corrosion cracking in 3.5 wt pct NaCl solution. AboveK _scelectroplated-zinc coatings do not appear to affect the crack-growth rate, although the incubation period prior to the onset of crack growth is reduced. Hot-dip zinc coatings increase stress corrosion crack growth rates slightly because of the additive effect of internal dissolved hydrogen. Hot-dip zinc coatings reduce the critical stress intensity for fracture in the absence of a corrosive environment because of embrittlement by internal hydrogen which is released from traps during hot-dip coating and confined by the inter metallic coatings which form on the steel surface in the hot dip bath. A simple fracture mechanics analysis indicates that either increasing diameter or the presence of a zinc coating lowers the critical hardness at which the stress corrosion cracking of structural bolts can occur.