Influence of tempering temperature on both the microstructural evolution and elemental distribution in AISI 4340 steels

In the present study, the influence of tempering temperature on the microstructural evolution and prior austenite grain boundary segregation of AISI 4340 steels was investigated by transmission electron microscope and atom probe. The transmission electron microscopy results showed a variation in the microstructure and the morphology of carbides with a change in tempering temperature. Additionally, the chemical compositions of the prior austenite grain boundaries and carbides were quantified by atom probe tomography. An increase in the tempering temperature led to a decrease in the amount of carbon segregated at the prior austenite grain boundary from 7.9 to 1.3 at.%. It was found that a higher tempering temperature can accelerate the diffusion of carbon from the prior austenite grain boundary into carbide. However, phosphorus atoms were segregated mainly at the prior austenite grain boundary in steel tempered at 400°C (up to 0.18 at.%). It was found that formation of film-like carbide and phosphorus segregation along the prior austenite grain boundary is the main cause of embrittlement in steel tempered at 400°C.     

离子渗碳层中的晶间脆性SCIEI

本文对20Cr2Ni4A钢离子渗碳层出现的沿晶断裂的原因进行了分析,结果表明,渗碳层中的残余奥氏体与在该区域产生的沿晶脆断无关。TEM分析和Auger电子能谱分析表明,形成沿晶断裂的主要原因是S,P等杂质元素在原奥氏体晶界的偏聚。采用二次加热淬火可以消除这种现象。     

Intergranular fracture in high chromium heat-resistant steel

The grain boundary segregation of impurities, especially phosphorus, and the fracture behavior of 12Cr heatresistant steel have been investigated. Temper embrittlement caused by phosphorus at grain boundaries was observed at a temperature below 750°C. Phosphorus at the grain boundaries increased as tempering temperature decreased, which changed the fractrure mode from trans- to intergranular. The segregation free energy of phosphorus was evaluated asδG _segrδH_segr- TδS_segr=- 24,900-48.2T (Jmol^-1). The enhanced concentration of phosphorus at the grain boundaries is due to the decrease in carbon activity by the chromium addition rather than the synergistic cosegregation of chromium and phosphorus.     

Si-Mn-Mo系低碳贝氏体钢焊接热影响区的脆化机理

用焊接热模拟,普通光学金相,透射、扫描电镜及电子探针,X射线和常规拉伸、冲出等手段研究了一种新型Si-Mn-Mo系低碳贝氏体钢焊接热影响区过热区的组织和性能的关系,重点探讨了过热区的脆化机理.结果表明,在焊接热模拟条件下,原始奥氏体晶粒尺寸是影响机械性能的主要因素.少量准下贝氏体与低碳马氏体的混合组织具有最佳的强韧性配合.随线能量增加,影响韧性的主要因素是奥氏体晶粒粗化以及高温时碳原子在奥氏体晶界及其附近的偏聚;而且碳原子的这种偏聚是经过较高线能量热循环后出现沿晶脆性断口的主要原因.粒状贝氏体及粒状组织中的M-A岛不是该钢焊接热影响区过热区脆化的原因.     

INTERGRANULAR EMBRITTLEMENT IN PLASMA CARBURIZED LAYER

This paper deals with the cause of intergranular fracture occurred in the retained austeniticregion in plasma carburized layer.The results show that the presence of retained austenite,which has a good effect on the impact toughness,has no relation to this embrittlement.Analy-sis by Auger electron spectroscopy shows that the impurities S and P segregate at the grainboundaries is the main reason of the intergranular embrittlement in carburized layer.However,the segregation of P and S can be removed by reheating and quenching treatment.     

Kinetics of phosphorus segregation at grain boundaries of low-alloy low-carbon steel

In a temperature range of 280–320°C, the mechanism and kinetics of segregation of impurities in steels have yet remained insufficiently studied. Under these conditions diffusion of impurities in the bulk of steel grains practically ceases, and for describing the kinetics of the process it is incorrect to use the Langmuir-McLean equation. In this work we put forward two new approaches to describe the mechanism and kinetics of phosphorus segregation in steels: a model of sequential changes in the state of phosphorus based on first-order reactions and a model of diffusion redistribution of phosphorus between boundaries of carbide precipitates, structure defects, and boundaries of steel grains. A comparative analysis of the suggested models has been conducted, and estimates of the kinetics of segregation based on them have been made; these estimates have been compared with the experimental results obtained in the temperature range of 280–320°C for test times to ～20 years. It has been shown that these models fairly well describe the experimental kinetics of phosphorus segregation in boundaries of steel grains.     

Roles of bulk carbon content on grain size,carbide reactions and intergranular rupture life in 2.25cr martensitic heat resistant steels

The steel of a higher bulk carbon content shows the denser precipitation distribution of carbides after the solution treatment followed by tempering. Such a carbide distribution produces the smaller prior austenite grain size after the welding simulation at a high temperature. Because the equilibrium segregation concentration of phosphorus decreases with decreasing prior austenite grain size, the specimen of the higher bulk carbon content shows therefore the longer intergranular rupture life. The rupture life is also increased by the partitioning of phosphorus pre-segregated at prior austenite grain boundary/carbide interfaces onto the fresh surface of precipitates formed on the surface of pre-formed carbides. The intergranular rupture life is additionally increased by the repulsive segregation between carbon and phosphorus which decreases the overall phosphorus segregation concentration at the prior austenite grain boundaries.     

Temper embrittlement of structural alloy steels (review)

Conclusion An analysis of the literature data from recent years shows that in spite of the widespread application of modern high-resolution research methods yielding quantitative data on the composition of grain-boundary segregations of dopants and alloying elements, the problem of the mechanism of reversible temper embrittlement remains open. In particular, one of the fundamental questions of the theory of temper embrittlement remains controversial: the question of the role of alloying elements, especially of molybdenum which, when used as dopant, reduces the susceptibility to temper embrittlement.Practically all the hitherto suggested models of temper embrittlement explain the effect of carbide-forming elements (Cr, Mn, Mo) by stating that when they are added to steel, the content of the impurity (phosphorus) on the grain boundaries changes. However, this is not always confirmed. In [36, 38, 54] it was shown that an addition of molybdenum reduces the susceptibility to temper embrittlement with unchanged phosphorus concentration on the grain boundaries, and increased content of Cr, Mn (and also of Ni) does not cause the phosphorus content on the grain boundaries to increase. To explain the role of alloying elements and of phosphorus, the authors of [55] were the first to resort to calculations of quantum mechanics, and as a result they concluded that the cause of increased embrittlement upon alloying with chromium are the weakened metal-metal bonds on the grain boundaries caused by the different electronegativity of phosphorus in relation to iron and the alloying elements.It seems that shedding light on the effect of alloying elements and dopants on the type and strength of the chemical bonds at the grain boundaries will henceforth play an important part in the understanding of the process of reversible temper embrittlement of alloy steels.Physictechnical Institute, Ural Scientific Center, Academy of Sciences of the USSR, Ustinov. Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 1, pp. 24–32, January, 1987.     

Grain Boundary Segregation Behavior in 2.25Cr-1Mo Steel During Reversible Temper Embrittlement

Low alloy steels serving for a long time at high temperature, e.g., around 500 °C, are very sensitive to temper embrittlement due to segregation of various trace elements at prior austenite grain boundaries and/or carbide/matrix interfaces. This type of segregation in combination with various environmental effects can adversely affect the fracture resistance and fatigue crack propagation rate with subsequent change in fracture morphology of low alloy steels. This article describes the segregation behavior of various elements in 2.25Cr-1Mo pressure vessel steel investigated by AES, FEG-STEM, SEM, and EDS analyses. As confirmed by AES and FEG-STEM, phosphorus is found to be the main embrittling element for isothermal embrittlement. Sulfur and Mo segregation is only evident after longer embrittlement times. In the step-cooling embrittlement, phosphorus is still found to be the main embrittling element, but heavy segregation of sulfur in some isolated intergranular facets was also observed. For P segregation, a Mo-C-P interaction is observed, while sulfur segregation is attributed to site competition between sulfur and carbon atoms.     

Grain boundary embrittlement by Mn and eutectoid reaction in binary Fe–12Mn steel

The grain boundary embrittlement in a binary Fe–12Mn is due to the grain boundary segregation of Mn. During tempering at 400 °C (higher than the equilibrium eutectoid reaction temperature 247 °C), reverted austenite particles were formed at lath and grain boundaries through the equilibrium reaction of lath martensite to ferrite + austenite. Surprisingly, hydrostatic pressure, which is induced by the transformation of epsilon martensite to austenite during heating at the tempering temperature, resulted in the nonequilibrium eutectoid reaction producing α-Mn precipitates at the interface between lath martensite and the transformed austenite during the tempering. The segregation concentration kinetics of Mn formed a convex profile due to the active grain boundary precipitation of the reverted austenite particles and the α-Mn particles, which act as a sink for the segregated Mn. Finally, the convex segregation profile of Mn corresponded to the concave profile of intergranular fracture strength.     

Maragin behavior of an Fe-19.5Ni-5Mn alloy. III: Mechanical properties

A high maraging strength in Fe-Ni-Mn alloys can be achieved at the expense of a marked loss in ductility. Very fine precipitates are observed when peak strength is reached. At peak strength, the Fe-Ni-Mn alloys exhibit brittle failure, mainly along prior austenite grain boundaries, irrespective of the nickel content. The presence of a small amount of retained austenite prior to aging does not improve the ductility. Previous explanation of the embrittlement in Fe-Ni-Mn alloys was attributed to the segregation of Mn to prior austenite grain boundaries. However, this is not fully supported by the present studies. Auger electron spectroscopy reveals no decisive evidence of manganese segregation. Some degree of ductility in the aged martensite may be required in order to prevent brittle fracture. Dual aging recovers part of the ductility and improves the strength slightly. The effect of reversed austenite on ductility may vary, depending on its morphology. Matrix and recrystallized austenite are beneficial to both elongation and reduction of area, but lathlike austenite lowers the elongation, probably because of its lamellar morphology. The lamellar structure of the lath martensite is also detrimental to elongation.     

THE SEGREGATION OF SULFUR AND PHOSPHORVS IN NICKEL-BASE ALLOY 718

1.IntroductionSurfaceandinterfacialsegregationiscurrentlyaveryactiveareaofresearch.Thisphenomenonhasbeenstudiedextensivelyinbinaryandternaryalloysll--31.Commercialsteelsandsuperalloysarecomplexsystemswithmanyelementalspecies.Whileimpuritysegregationhasbeenwidelystudiedinsteels,comparativelylittleisknownaboutthesuperalloys.Cleansuperalloyproductionisvanguardofthesuperalloyindustryandcleanlinesshasbeenbasicallyconsidetedintwocategories:inclusionsanddetrimentalelementsco.t.oll4].Sulfurandphospho…     

Atom probe investigations on temper embrittlement and reversible temper embrittlement in S 690 steel weld metal

Severe embrittlement was observed in weld material of a brand new penstock of a huge hydro power plant. Temper embrittlement (TE) was found as root case of embrittlement. Reversible temper embrittlement (RTE) treatment characterised by a short-time heating at about 600°C, by which the toughness of embrittled weld material can significantly be recovered, was qualified and successfully applied in the plant. Basic investigations were performed to explain the embrittlement as well as the de-embrittlement effect. By the application of high resolution analytics as Atom Probe Tomography (APT) applied on TE as well as on the RTE-treated material, revealed phosphorus segregation in the grain boundaries as root cause of embrittlement. By application of RTE treatment the APT results revealed, that the phosphorus segregation in the grain boundaries disappeared. The mechanism of this behaviour can be explained by referring the McLean [Grain boundaries in metals. Oxford: Clarendon Press; 1957] based grain boundary equilibrium segregation of phosphorous. During RTE treatment, which occur at higher temperatures (600°C) that segregation (which starts during cooling at about 550°C), desegregation occurs. During this higher temperature, the diffusion is much faster than segregation producing the fast recovery of toughness.     

THE NON-EQUILIBRIUM SEGREGATION OF BORON TO AUSTENITE GRAIN BOUNDARIES

采用高分辨率的径迹显微照相技术,研究了淬火硼钢中硼向奥氏体晶界偏聚的规律,定量地测定出跨过奥氏体晶界的硼的成分剖面图以及非平衡晶界偏聚的特征参量(晶界贫硼区宽度、晶界富集程度和富集带宽度)。试验表明,这种偏聚具有如下特征: 在偏聚晶界的两侧存在有一定宽度的贫硼区,晶界偏聚的硼是在冷却过程中由该区富集而来;这种偏聚对冷却速度很敏感,急速冷却可以抑制这种偏聚。冷却速度降低,晶界偏聚由连续的偏聚带,逐步发展为不连续的聚集直至明显地析出硼相,贫硼区宽度与冷却速度的平方根成反比;它的温度关系与晶界平衡偏聚预言相反,随淬火温度升高,晶界偏聚程度与贫硼区宽度增加。 通过试验,论证了淬火钢中硼向奥氏体晶界的偏聚,是在冷却过程中发生的一种非平衡的晶界偏聚现象。     

固溶温度对超纯净18Ni(350)马氏体时效钢断裂韧性及微观组织的影响

研究了在1083—1483K温度范围内，固溶温度对超纯净18Ni(350)马氏体时效钢断裂韧性(KIC)的影响．通过透射电镜(TEM)研究了马氏体时效钢微观组织的变化，结合相变曲线和断口扫描电镜(SEM)观察，探讨了固溶温度对断裂韧性的影响机理．结果表明：超纯净马氏体时效钢的断裂韧性(KIC)随着固溶温度的升高或再结晶晶粒尺寸的长大而增加，不存在常见的Ti(C，N)在晶界偏聚而引起的“热脆”现象．固溶态马氏体时效钢由单一的马氏体板条组成，其形貌、间距以及位错密度不受固溶温度的影响．在时效过程中，随着固溶温度的升高或再结晶晶粒的粗化，Ni3(Mo，Ti)等时效析出相在晶界或板条界的偏聚程度逐渐加重并导致基体软化，合金元素Ni，Mo的富集诱发了逆转变奥氏体形成．这使裂纹尖端易于钝化而表现出韧窝状穿晶断裂和保持较高的断裂韧性．     

Change in the ductility properties of 2.25 Cr-1 Mo steel during post-welding heat treatment

A major problem associated with the use of steels at elevated temperatures in the chemical, petrochemical and power industries, is not only that of hydrogen embrittlement and creep, but also the loss of ductility related to the content of low-alloy trace elements. This phenomenon is known as temper embrittlement. Temper brittleness is associated with embrittlement due to heat treatment, rather than that due to a long period of exposure to high temperatures under working conditions. Since Polish technical literature does not have a term describing this phenomenon, the authors will use the expression 'loss of ductility' or 'working brittleness'. This particular embrittlement is caused by the segregation of phosphorus, tin, antimony and arsenic on the grain boundaries of the primary austenite during prolonged working life, or a low rate of cooling of the steel within the temperature range of 550 to 350°C. It manifests itself in the lowering of the impact strength or in the rising of the brittle fracture transition temperature (Fig.1).     

Intergranular fracture on fatigue fracture surface of 2.25Cr-1Mo steel at room temperature in air

Low-alloy steels serving for a long time at high temperature (∼500 °C) are very sensitive to temper embrittlement due to segregation of various trace elements at prior austenite grain boundaries and/or carbide/matrix interfaces. This type of segregation in combination with various environmental effects can adversely affect the fracture resistance and fatigue crack propagation rate with subsequent change in the fracture morphology of low-alloy steels. The present work describes the effects of heat treatments on impurity element segregation and its subsequent effects on fatigue fracture behavior of 2.25Cr-1Mo steel under different environmental conditions and temperatures. It has been found that either prior impurity element segregation caused during the heat treatment or hydrogen-induced embrittlement due to the presence of water vapor in laboratory air alone cannot produce intergranular fracture on the fatigue surfaces of 2.25Cr-1Mo steel at room temperature in air. The occurrence of intergranular fracture on the fatigue surfaces results from the combined effect of impurity element segregation-induced grain boundary embrittlement and hydrogen-induced embrittlement, and that the proportion of intergranular fracture is a function of prior impurity element segregation provided that the grain boundary segregation level exceeds a certain critical value.     

国产06Ni9DR 钢焊接热影响区组织和低温韧性

采用扫描电镜(SEM)、背散射电子衍射(EBSD)和焊接热模拟技术,研究了单次热循环不同峰值温度对国产06Ni9DR 钢焊接热影响区(HAZ)显微组织和低温冲击韧性的影响. 结果表明,06Ni9DR 钢HAZ的-196 ℃冲击吸收能量均低于母材,HAZ整体发生了脆化. 粗晶区脆化最为严重,原因是原始奥氏体晶粒粗大及其导致的有效大角度晶界较少,残余奥氏体量少且不稳定,以及较大的位错密度和粗大马氏体的存在. 晶界呈链状分布的大块逆转奥氏体和M-A组元的存在导致回火区脆化程度仅次于粗晶区. 细晶区和不完全脆化区的韧性低于母材,主要是因为淬火马氏体的存在和残余奥氏体的低温稳定性差.     

Observations of grain boundary impurities in nanocrystalline Al and their influence on microstructural stability and mechanical behaviour

The exceptional properties of nanocrystalline materials lend themselves to a wide range of structural and functional applications. There is recent evidence to suggest that grain boundary impurities may have a dramatic effect on the stability, strength and ductility of nanocrystalline metals and alloys. In this study, transmission electron microscopy and atom probe tomography were used to characterize specimens deposited at different base pressures, thus providing a direct comparison of impurity content with microstructural stability and mechanical behaviour. Atom probe measurements provide clear experimental evidence of grain boundary segregation of oxygen in samples deposited at higher base pressures. It is proposed that these oxygen atoms pin the boundaries, preventing stress-assisted grain growth and resulting in increased strength and loss in ductility. This study provides the first direct experimental evidence that boundary impurities play a critical role in determining the microstructural stability and deformation behaviour of nanocrystalline metals.