Evolution and Coarsening of Carbides in 2.25Cr-1Mo Steel Weld Metal During High Temperature Tempering

Transformation and coarsening of carbides in 2.25Cr-1Mo steel weld metal during tempering at 700 ℃ for different time intervals ranging from 1 to 150 h were examined by transmission electron microscopy and scanning electron microscopy. M3C carbides were observed in the as-welded specimens and when tempered, the precipitates were mainly composed of M3C, M7C3, and M23C6 carbides. A sequence for corresponding carbide transformation during tempering with initial precipitation of M3C and the subsequent precipitation of M7C3 and M23C6 was proposed. The precipitation of M7C3 with higher chromium content was the main factor contributing to the decrease in coarsening rate of precipitates after prolonged tempering. The decrease in hardness of the tempered specimens agreed well with the prediction of the weakening of precipitation strengthening owing to the coarsening of carbides.     

钼钨钒合金化热作模具钢高温回火组织演变

为适应热冲压技术的发展需求,开发了一种新型高热导率高耐磨性能热冲压用模具钢材料。采用扫描电镜（SEM）、透射电镜（TEM）等检测手段对钼钨钒合金化新型模具钢的高温回火性能与组织特征进行了研究。阐明了新型热冲压模具钢回火过程碳化物析出与演变规律。实验结果表明:实验用钼钨钒合金化模具钢材料具有良好的回火二次硬化性能,在500～600 ℃温度区间回火时,回火组织硬度上升;在600 ℃回火出现二次硬化峰值;当回火温度超过600 ℃后,组织软化程度明显,回火硬度开始下降。实验模具钢在高温回火过程中的硬度变化与其合金碳化物的偏聚、析出和聚集长大密切相关。当在560 ℃以下回火时,实验钢组织中未有合金碳化物析出;当回火温度大于560 ℃时,回火组织中开始析出M₂C型碳化物;当回火温度高于600 ℃后开始析出MC型碳化物;当在620 ℃长时间回火后M₂C型碳化物转化为M₆C型碳化物,此时实验钢硬度开始明显下降;而当回火温度高于660 ℃时,新型实验钢组织中主要为M₆C和MC型合金碳化物。      

抗氢2.25Cr-1Mo钢热处理工艺与性能研究

本文主要研究了2.25C r-1M o钢正火处理后显微组织和回火过程中碳化物相对钢的强韧性的影响,奥氏体化处理后进行冷却(加速冷却和空冷),得到的显微组织为粒状贝氏体和先共析铁素体。对于2.25C r-1M o厚钢板,显微组织和碳化物相的变化是造成2.25C r-1M o钢强韧性能变化的主要原因。     

Precipitation Reactions during the Heat Treatment of Ferritic Steels

The precipitation reactions in two ferritic steels, 9Cr-1Mo-V-Nb and 12Cr-1Mo-V-W, were studied. Analytical electron microscopy, optical microscopy, electrolytic extractions, and hardness measurements were used to determine the types, amounts, and effects of precipitates formed as a function of the heat treatment. The effect of variations in the austenitizing treatment was ascertained. In addition to variations in the austenitizing time and temperature, different cooling rates after austenitization were also used. Air cooling after austenitization (normalization) resulted in little precipitation in both alloys. Precipitation in the 12Cr-1Mo-V-W alloy after furnace cooling was found in all cases examined. Under certain conditions precipitation was also found after furnace cooling the 9Cr-1Mo-V-Nb alloy. However, when compared to the amount of precipitate in the fully tempered state, the 9Cr-1Mo-V-Nb showed a much greater variation in the degree of precipitation following furnace cooling. In addition, the matrix microstructure of the 9Cr-1Mo-V-Nb alloy was very sensitive to cooling rate. The precipitation reactions during tempering after a normalizing treatment were followed as a function of tempering treatment. Tempering temperatures were varied from 400 to 780 °C. The carbide precipitation was essentially complete after one hour at 650 °C for both alloys. Analytical microscopy was used to identify the precipitates. In the 9Cr-1Mo-V-Nb alloy, a combination of chromium-rich M₂₃C₆ and vanadium-niobium-rich MC carbides was found. The carbides in the 12Cr-1Mo-V-W alloy were identified as chromium-rich M₂₃C₆ and vanadium-rich MC. The results give an indication of the sensitivity of these alloys to heat treatment variations. This paper is based on a presentation made at the “Peter G. Winchell Symposium on Tempering of Steel” held at the Louisville Meeting of The Metallurgical Society of AIME, October 12-13, 1981, under the sponsorship of the TMS-AIME Ferrous Metallurgy and Heat Treatment Committees.     

Tempering of 2.25 Pct Cr-1 Pct Mo Low Carbon Steels

The effect of carbon level on the tempering behavior at 700°C of 2.25 pct Cr-1 pct Mo steels having typical weld metal compositions has been investigated using analytical electron microscopy and X-ray diffraction techniques. The morphology, crystallography and chemistry, of each of the various types of carbides observed, has been established. It has been shown that each carbide type can be readily identified in terms of the relative heights of the EPMA spectra peaks for iron, chromium, molybdenum, and silicon. A decrease in the carbon level of the steel increases the rate at which the carbide precipitation reactions proceed, and also influences the final product. Of the carbides detected, M₂₃C₆ and M₇C₃ were found to be chromium-based, and their compositions were independent of both the carbon level of the steel and the tempering time. The molybdenum-based carbides, M₂C and M₆C, however, showed an increase in their molybdenum contents as the tempering time was increased. The rate of this increase became greater as the carbon content of the steel was lowered.     

Effect of molybdenum on the fracture characteristic of high-speed steel quenched matrix

The fractures of three model alloys, imitating by their chemical composition the matrixes of the quenched high-speed steels of various Mo: W relations were analyzed. According to the measurements of the stress intensity factor K_Ic and the differences in the precipitation processes of carbides it was found out that the higher fracture toughness of the matrix of the molybdenum high-speed steels than on the tungsten ones is the results of the differences in the kinetics of precipitation from the martensite matrix of these steels during tempering. After tempering at 250 and 650°C the percentage of the intergranular fracture increases with the increase of the relation of Mo to W in the model alloys of the high-speed steel matrix. This is probably the result of higher precipitation rate of the M₃C carbide (at 250°C) and the MC and M₆C carbides (at 650°C) in the privileged regions along the grain boundaries. The change of the character of the model alloy fractures after tempering at 450°C from the completely transgranular one in the tungsten alloy to the nearly completely intergranular one in the molybdenum alloy indicates that the coherent precipitation processes responsible for the secondary hardness effect in the tungsten matrix begin at a lower temperature than in the molybdenum matrix. After tempering for the maximum secondary hardness the matrix fractures of the high-speed steels reveal a transgranular character regardless the relation of Mo to W. The higher fracture toughness of the Mo matrix can be the result of the start of the coherent precipitation processes at a higher temperature and their intensity which can, respectively, influence the size of these precipitations, their shape and the degree of dispersion. The transgranular character of the fractures of the S 6-5-2 type high-speed steel in the whole range tempering temperatures results from the presence of the undissolved carbides which while cracking in the region of stress concentration can constitute flaws of critical size which form the path of easy cracking through the grains. The transgranular cracking of the matrix of the real high-speed steels does not change the adventageous influence of molybdenum upon their fracture toughness. On the other hand, the carbides, undissolved during austenitizing, whose size distribution in the molybdenum steels from the point of view of cracking mechanics seems to be unsatisfactory, influence significantly the fracture toughness of these steels.     

2.25Cr-1Mo合金钢回火脆化过时效现象的研究

研究了2.25Cr-1Mo合金钢在回火温度下时效处理时,发生回火脆化和回火脆化的过时效反偏聚现象。应用非平衡偏聚的动力学理论,确定了成分(%)为0.15C、2.32Cr、0.95Mo、0.009P的2.25Cr-1Mo合金钢在650℃140 h回火时钢中磷的非平衡晶界偏聚规律。试验得出,2.25Cr-1Mo合金钢650℃磷非平衡偏聚的临界时间t_c为20 h,晶界磷的原子浓度,由初始状态的0.016%提高至最大值2.79%。根据试验数据进行的动力学计算,得出的计算曲线与试验结果吻合,验证了非平衡晶界偏聚空位-复合体模型的扩散机制。     

Carbide Precipitation in 2.25 Cr-1 Mo Bainitic Steel: Effect of Heating and Isothermal Tempering Conditions

The effect of the tempering heat treatment, including heating prior to the isothermal step, on carbide precipitation has been determined in a 2.25 Cr-1 Mo bainitic steel for thick-walled applications. The carbides were identified using their amount of metallic elements, morphology, nucleation sites, and diffraction patterns. The evolution of carbide phase fraction, morphology, and composition was investigated using transmission electron microscopy, X-ray diffraction, as well as thermodynamic calculations. Upon heating, retained austenite into the as-quenched material decomposes into ferrite and cementite. M₇C₃ carbides then nucleate at the interface between the cementite and the matrix, triggering the dissolution of cementite. M₂C carbides precipitate separately within the bainitic laths during slow heating. M₂₃C₆ carbides precipitate at the interfaces (lath boundaries or prior austenite grain boundaries) and grow by attracting nearby chromium atoms, which results in the dissolution of M₇C₃ and, depending on the temperature, coarsening, or dissolution of M₂C carbides, respectively.     

An assessment of creep deformation and fracture behavior of 2.25Cr-1Mo similar and dissimilar weld joints

The evaluation of the creep deformation and fracture behavior of a 2.25Cr-1Mo steel base metal, a 2.25Cr-1Mo/2.25Cr-1Mo similar weld joint, and a 2.25Cr-1Mo/Alloy 800 dissimilar weld joint at 823 K over a stress range of 90 to 250 MPa has been carried out. The specimens for creep testing were taken from single-V weld pads fabricated by a shielded metal arc-welding process using 2.25Cr-1Mo steel (for similar-joint) and INCONEL 182 (for dissimilar-joint) electrodes. The weld pads were subsequently given a postweld heat treatment (PWHT) of 973 K for 1 hour. The microstructure and microhardness of the weld joints were evaluated in the as-welded, postweld heat-treated, and creep-tested conditions. The heat-affected zone (HAZ) of similar weld joint consisted of bainite in the coarse-prior-austenitic-grain (CPAG) region near the fusion line, followed by bainite in the fine-prior-austenitic-grain (FPAG) and intercritical regions merging with the unaffected base metal. In addition to the HAZ structures in the 2.25Cr-1Mo steel, the dissimilar weld joint displayed a definite INCONEL/2.25Cr-1Mo weld interface structure present either as a sharp line or as a diffuse region. A hardness trough was observed in the intercritical region of the HAZ in both weld joints, while a maxima in hardness was seen at the weld interface of the dissimilar weld joint. Both weld joints exhibited significantly lower rupture lives compared to the 2.25Cr-1Mo base metal. The dissimilar weld joint exhibited poor rupture life compared to the similar weld joint, at applied stresses lower than 130 MPa. In both weld joints, the strain distribution across the specimen gage length during creep testing varied significantly. During creep testing, localization of deformation occurred in the intercritical HAZ. In the similar weld joint, at all stress levels investigated, and in the dissimilar weld joint, at stresses ≥150 MPa, the creep failure occurred in the intercritical HAZ. The fracture occurred by transgranular mode with a large number of dimples. At stresses below 150 MPa, the failure in the dissimilar weld joint occurred in the CPAG HAZ near to the weld interface. The failure occurred by extensive intergranular creep cavity formation.     

Evolution of Carbide Precipitates in 2.25Cr-1Mo Steel during Long-Term Service in a Power Plant

Carbide precipitation from the steel matrix during long-term high-temperature exposure can adversely affect the fracture toughness and high-temperature creep resistance of materials with implications on the performance of power plant components. In the present work, carbide evolution in 2.25Cr-1Mo steel after long-term aging during service was investigated. Boiler pipe samples of this steel were removed from a supercritical water-cooled coal-fired power plant after service times of 17 and 28 years and a mean operational temperature of 810 K (537 °C). The carbide precipitation and coarsening effects were studied using the carbon extraction replica technique followed by analysis using transmission electron microscopy and energy dispersive X-ray spectroscopy. The carbides extracted using an electrolytic technique were also analyzed using X-ray diffraction to evaluate phase transformations of the carbides during long-term service. Small ball punch and Vickers hardness were used to evaluate the changes in mechanical performance after long-term aging during service.     

热处理工艺对新型Cr8Mo2VSi和D2冷作模 具钢扁钢组织和力学性能的影响

 研究了热处理工艺对高碳、高铬冷作模具钢Cr8Mo2VSi和D2钢的组织和性能的影响,结果表明：Cr8Mo2VSi比D2钢的碳化物更细小、均匀;1020～1040 ℃淬火,Cr8Mo2VSi的硬度略低于D2,经高温回火后,Cr8Mo2VSi钢表现出更好的二次硬化效应,其硬度高于D2钢1~2（HRC）,并且比D2钢具有更好的强、韧性配合。     

The effect of tungsten on dislocation recovery and precipitation behavior of low-activation martensitic 9Cr steels

The effect of W on dislocation recovery and precipitation behavior was investigated for martensitic 9Cr-(0,l,2,4)W-0.1C (wt pct) steels after quenching, tempering, and subsequent prolonged aging. The steels were low induced-radioactivation martensitic steels for fusion reactor structures, intended as a possible replacement for conventional (7 to 12)Cr-Mo steels. During tempering after quenching, homogeneous precipitation of fine W₂C occurred in martensite, causing secondary hardening between 673 and 823 K. The softening above the secondary hardening temperature shifted to higher temperatures with increasing W concentration, which was correlated with the decrease in self-diffusion rates with increasing W concentration. Carbides M₂₃C₆ and M₇C₃ were precipitated in the 9Cr steel without W after high-temperature tempering at 1023 K. With increasing W concentration, M7C3 was replaced by M₂₃C₆, and M₆C formed in addition to M₂₃C₆. During subsequent aging at temperatures between 823 and 973 K after tempering, the recovery of dislocations, the agglomeration of carbides, and the growth of martensite lath subgrains occurred. Intermetallic Fe₂W Laves also precipitated in the δ-ferrite grains of the 9Cr-4W steel. The effect of W on dislocation recovery and precipitation behavior is discussed in detail.     

The evaluation of in-service materials degradation of low-alloy steels by the electrochemical method

The nondestructive evaluation procedure for detecting in-service materials degradation of low-alloy 2.25Cr-1Mo and CrMoV steels by the electrochemical method has been investigated. The results can be summarized as follows. (1) For 2.25Cr-1Mo steels, the peak current mainly caused by the selective dissolution of coarse carbides M₆C appears at ∼+100 mV during potentiodynamic polarization measurements in dilute sodium molybdate solution. This peak value of current density, ΔI_p, can be chosen as a reflective parameter of an amount of coarse carbides M₆C and shows excellent correlations both with shifts in fracture appearance transition temperature (FATT) caused by carbide coarsening and with hardness change. Actual operational temperature can be estimated from operational period, since the Larson-Miller time-temperature parameter (LMP) value of materials has a unique relationship with ΔI_p values. (2) For CrMoV steels, the evaluation of temper embrittlement of CrMoV cast steel by a novel electrochemical technique is described. Intergranular corrosion (IGC) occurs only on temper-embrittled samples during anodic polarization process in calcium nitrate solution. The characteristic changes in polarization curves attributed to IGC have an excellent correlation with shifts in FATT caused by temper embrittlement.     

Effects of alloying additions and austenitizing treatments on secondary hardening and fracture behavior for martensitic steels containing both Mo and W

The effects of alloying additions and austenitizing treatments on secondary hardening and fracture behavior of martensitic steels containing both Mo and W were investigated. The secondary hardening response and properties of these steels are dependent on the composition and distribution of the carbides formed during aging (tempering) of the martensite, as modified by alloying additions and austenitizing treatments. The precipitates responsible for secondary hardening are M₂C carbides formed during the dissolution of the cementite (M₃C). The Mo-W steel showed moderately strong secondary hardening and delayed overaging due to the combined effects of Mo and W. The addition of Cr removed secondary hardening by the stabilization of cementite, which inhibited the formation of M₂C carbides. The elements Co and Ni, particularly in combination, strongly increased secondary hardening. Additions of Ni promoted the dissolution of cementite and provided carbon for the formation of M₂C carbide, while Co increased the nucleation rate of M₂C carbide. Fracture behavior is interpreted in terms of the presence of impurities and coarse cementite at the grain boundaries and the variation in matrix strength associated with the formation of M₂C carbides. For the Mo-W-Cr-Co-Ni steel, the double-austenitizing at the relatively low temperatures of 899 to 816 °C accelerated the aging kinetics because the ratio of Cr/(Mo + W) increased in the matrix due to the presence of undissolved carbides containing considerably larger concentrations of (Mo + W). The undissolved carbides reduced the impact toughness for aging temperatures up to 510 °C, prior to the large decrease in hardness that occurred on aging at higher temperatures.     

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.     

The effect of molybdenum on high-temperature properties of 9 pct Cr steels

Heat-resistant 9 Cr steels with 1, 2, and 3 pct Mo were tested for mechanical properties, weldability, and creep-rupture properties. The elevated-temperature and rupture strengths increase with increasing molybdenum content. While the 9 Cr-1 Mo steel is martensitic and is precipitation strengthened with carbides, the 9 Cr-2 Mo and 9 Cr-3 Mo steels receive added benefits from precipitation of Laves phase and solid-solution strengthening. The latter cause little decrease in ductility and impact resistance. The 9 Cr-2 Mo and 9 Cr-3 Mo steels are characterized by a duplex microstructure which aids weldability. Weld cracking tests show no need for preheating the latter steels, although the martensitic 9 Cr-1 Mo steel is known to be susceptible to weld cracking if not preheated. Both duplex-structure steels have good resistance to stress-relief cracking. Anisotropy of mechanical properties, due to the orientation of the duplex structure in the rolling direction, is less than that observed in the fully martensitic 9 Cr-1 Mo steel.     

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.     

Phase transformations during tempering of the Fe-15Cr-1Mo martensites containing nitrogen or carbon

Hardness measurements, dilatometry, internal friction measurements, Mössbauer spectroscopy and transmission electron microscopy are utilized in order to study the effect of tempering on the microstructure of a stainless martensitic steel containing 15% Cr, 1% Mo and 0.6% N. A similar carbon steel containing 15% Cr, 1% Mo and 0.6% C is used for comparison. Tempering of alloy Fe-15Cr-1Mo-0.6N in the low temperature range of 353-473 K leads to formation of hexagonal ?-nitride (Fe,Cr)₂N, which is followed by precipitation of the orthorombic ?-nitride (Fe,Cr)₂N at temperatures of 573-773 K. The hexagonal nitride Cr₂N is precipitated at 923 K and preferably formed at grain boundaries. The alloy Fe-15Cr-1Mo-0.6C shows the expected tempering behaviour. ?-carbide (Fe,Cr)₂C and cementite (Fe,Cr)₃C are precipitated during low temperature ageing, followed by the formation of Cr₇C₃ carbides after the temperature has risen to 873 K. With a similar interstitial content the amount of retained austenite in the nitrogen martensite is nearly twice as high as in the carbon one. Furthermore, the thermal stability of the retained austenite of the nitrogen alloy is substantially higher than that of the carbon steel.     

含氮Cr-W-Mo-V半高速钢回火过程中的沉淀析出行为

进行了Cr-W-Mo-V(%:46Cr-24W-24Mo-1.52.0V)系和Cr-W-Mo-V+N(0.05%0.10%)系半高速钢(Semi-HSS)1050℃淬火后分别在100~600℃两次回火沉淀析出行为的研究。采用透射电镜、扫描电镜及能谱仪和能量损失谱对碳化物形貌和成分进行分析,用X射线衍射法测定残余奥氏体的体积分数。结果表明,氮有增强钢的二次硬化的效果,氮促进碳氮化物在425~475℃回火析出,在550℃回火碳化物依附在氮化物表面而沉淀形成复合碳氮化物。Semi-HSS+N在淬火及400℃以下回火,残余奥氏体为15%~17%;随回火温度增加,残余奥氏体量急剧降低,在525℃回火残余奥氏体小于3%。