Phosphor in Eisen und Stahl – Ein Überblick über grenzflächenanalytische Untersuchungen am Max-Planck-Institut für Eisenforschung zum Segregationsverhalten des Phosphors an äußeren und inneren Grenzflächen von Eisen und Stahl

Phosphorus in iron and steel – An overview of surface analytical investigations of the segregation behaviour of phosphorus on internal and external iron and steel surfaces The surface segregation of phosphorus was studied on (100) oriented single crystals of the type Fe? P and Fe? Si-P. Phosphorus shows a strong tendency to enrich at surfaces. The interaction with lattice defects leads to an additional enrichment below the surface. A strong repulsive interaction of phosphorus with segregating silicon can lead to a complete displacement of silicon from the surface region. Equilibrium segregation experiments revealed a segregation enthalpy for phosphorus of ?180 kJ/mol for the ternary system Fe? Si? P, this is only slightly lower than the segregation enthalpy of the extremely surface active sulfur in iron anti steel. The strong tendency of phosphorus to enrich at interface in iron and steel is also observed for grain boundaries. The grain boundary segregation of phosphorus was studied for the systems Fe? P, FeC? P, Fe? M? P and Fe? M? C? P with M ? Cr, Mo, V, Ti, Nb. The segregation of carbon leads to the displacement of phosphorus. By the presence of carbide forming elements like chromium in the material this positive effect is reduced. Elements, that can tie up phosphorus, like titanium and intermetallic phases, that dissolve phosphorus, -an also reduce the segregation of phosphorus. addition ally a phosphorus segregation to the interface carbide/matrix was observed.     

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.     

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.     

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.     

Precipitation related anomalies in kinetics of phosphorus grain boundary segregation in low alloy steels

It has been shown that particles of M₆C in Cr–Mo–V low alloy steels can influence phosphorus grain boundary segregation in a similar manner to Laves phase particles in 12CrMoV steel. The influence of these particles arises from their ability to dissolve non- metallic elements such as phosphorus and silicon. As phosphorus is progressively segregated to the grain boundaries during prolonged ageing, the precipitation of M₆C particles leads to an anomalous decrease in the phosphorus grain boundary concentration as the ageing time is extended. This phenomenon originally observed for the Laves phase in long-term aged 12CrMoV steel at temperatures of 753, 773, and 803 K has now been observed for M₆C carbide in a 2.5Cr–0.4Mo–0.25V low alloy steel aged at 853 K.     

Fe-Cr-V耐磨堆焊合金

制备了用于埋弧焊药芯焊丝的Fe-Cr-V堆焊合金,其成份(质量分数,%)为c0.9～1.5,Cr 13～15,V 1.0-2.0.借助光学显微镜、扫描电镜和X射线衍射等手段,研究了其显微组织,并考察V和B4C含量对该堆焊合金性能的影响.Fe-Cr-V堆焊合金的显微组织由铁素体 马氏体 (Cr,Fe)23C6等碳化物组成.电子能谱微区分析显示Cr,V元素晶界含量显著高于晶内,随WC加入量提高,晶界与晶内含量差距增大.由于沿晶界析出碳化钒,这使(Cr,Fe)23C6等晶界碳化物呈条状或断续网状分布,起到耐磨骨架作用,避免了网状形态的强烈脆性.结果表明,其磨粒磨损性能显著优于实心焊丝H25Cr3Mo2MnV堆焊合金.     

On the role of carbon in molybdenum manufactured by Laser Powder Bed Fusion

Carbon is known to improve the ductility and grain boundary strength of molybdenum. Scientific consensus to explain this phenomenon is that carbon either replaces oxygen impurities at grain boundaries or suppresses the diffusion of oxygen towards the grain boundaries. The aim of this study is to clarify the mechanism on how the carbides interact with the oxygen impurities and the molybdenum matrix, thus to provide a better understanding for designing molybdenum alloy compositions. Molybdenum alloyed with 4500 μg/g carbon was manufactured in the additive manufacturing process of Laser Powder Bed Fusion (LPBF). The cellular grain structure of molybdenum cells with surrounding molybdenum carbide caused by constitutional undercooling during the solidification process was investigated by Transmission Electron Microscopy (TEM) for morphology, composition and crystal structure. The carbide was identified to be orthorhombic ζ-Mo₂C, which has a solubility for oxygen. ζ-Mo₂C shows a semi-coherent interface with α-Mo. No cracks could be found at the α-Mo / α-Mo or the α-Mo / ζ-Mo₂C interfaces. Oxygen could not be detected at grain boundaries, but only within ζ-Mo₂C, which traps the oxygen, thus avoiding oxygen segregation to the grain boundaries and improving the grain boundary strength.     

Microstructural Factors That Decrease the Local Strength of Grain Boundaries in Martensitic Steels

As a result of the phase transformation of austenite to martensite during steel quenching, weakened structural regions, specifically the boundaries of the original austenite grains, have been formed. They are weakened because of microstructural factors, such as the residual internal microstrains and segregation of embrittling impurities. The joint effect of microstructural factors, namely, residual microstrains and segregation of phosphorus and carbon at grain boundaries, on reducing the local strength of the boundaries of the initial austenite grains in martensitic steels is quantitatively evaluated, and the impacts of these microstructural factors have been separated. The dependences of the local grain-boundary strength on the ratio of various levels of residual microstrains and on the atomic concentration of phosphorus impurities at the grain boundary in segregation spots have been determined. It has been shown quantitatively that the adsorption enrichment of the austenite grain boundaries with phosphorus leads to a decrease in the intergrain adhesion and facilitates the emergence and development of cracks along the boundaries of the initial austenite grains. The quantitative dependence of the local strength of grain boundaries on the concentration ratio of carbon and phosphorus in them has been shown. Carbon in concentrations of up to 0.04% reduces the embrittlement of the boundaries due to the segregation of phosphorus and loses its neutralizing effect on the phosphorus segregation at concentrations of more than 0.04%, so the phosphorus concentration at the grain boundaries increases and the embrittlement resistance of the latter decreases. The applicability of the developed technique for the quantitative evaluation of the local strength of hardened steel grain boundaries by using tests on delayed fracture and applying the method of finite elements to determine the local strains has been shown.     

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

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

Grain boundary segregation and intergranular fracture in Ferrite containing Mo,Si or Al

Roles of molybdenum, silicon or aluminum in ferrite on grain boundary segregation and hence on intergranular fracture have been investigated by using Auger electron spectroscopy (AES) and tensile test. Competitive segregation between sulfur and carbon or nitrogen, which caused the decrease below 700°C of sulfur content at the grain boundaries, was observed in the pure iron. The intergranular brittleness of the pure iron was caused by sulfur at the grain boundaries. When molybdenum was added to the pure iron, the sulfur contents at the grain boundaries were lowered in comparison to those in the pure iron. The molybdenum-bearing alloy showed higher fracture strength than that of the pure iron, and fractured mostly in the transgranular mode. This arises from the intrinsic effect of molybdenum on the grain boundaries as well as the decrease in sulfur content. Tn the 3.37 wt.%Si alloy, silicon and carbon or nitrogen competitively segregated to the grain boundaries, and such a competitive segregation was also observed between sulfur and carbon or nitrogen. The sulfur content at the grain boundaries decreased with increasing silicon content. The fracture modes in the 3.37- and 4.26 wt.%Si alloys were transgranular in the rolling direction, but were mostly intergranular in the transverse direction and in the as-rolled condition. The intergranular characteristic in the fracture behavior may be attributed to the detrimental effect of silicon as well as sulfur on the intergranular cohesion. Carbon and aluminum only were found at the grain boundaries of the aluminum-bearing alloy. This suggests that aluminum is a strong repulser of sulfur or nitrogen at the grain boundaries. Additionally, it was found that aluminum has a detrimental effect on grain boundary strength of ferrite.     

Intergranular corrosion of iron-phosphorus alloys in nitrate solutions

The corrosion of Fe-P alloys with 0.003–2.5 wt.%P has been studied in hot nitrate solutions. The current-potential curves show an extended active range and increased corrosion currents for high phosphorus alloys. The alloy with 2.5P does not passivate at all. The other alloys have been tested for intergranular corrosion in the passive range at 1,000 mV(SHE). The intergranular attack increases with increasing phosphorus content and can be correlated to its grain boundary concentration. The grain boundary concentrations had been established by equilibrium segregation at temperatures between 400 and 80°C and were determined by Auger electron spectroscopy (AES). The presence of phosphorus in solid solution and segregated to the grain boundaries prevents the formation of a passive layer on iron, if its local concentration is higher than ca. 2–3 at.%.     

镁偏析对铝合金晶界性能影响的计算机模拟

采用嵌入原子法对铝晶界上Mg的偏析性质及其对晶界性能的影响进行了计算机模拟。结果表明 ,Mg的晶界偏析具有自发性 ,并且降低基体的电荷密度和空位形成能 ,从而导致晶界脆化。     

Effect of alloying elements on fracture behavior of Fe-18Ni-2Ti-(8Co) alloys

Effect of alloying elements on fracture behavior of Fe-18Ni-2Ti-(8Co) alloys has been investigated in the light of grain boundary segregation of alloying elements. During isothermal aging at 540°C, hardness level in the cobalt-bearing alloy was higher than that in the cobalt-free alloy, which is attributed to the solid solution hardening of cobalt, and the bigger hardness difference after overaging was due to the relatively fine precipitates in the cobalt-bearing alloy. The grain boundary segregation behavior of the elements was similar in two alloys, regardless of the cobalt addition. In two alloys, the fracture behavior before and after the maximum tensile strength is mainly governed by two factors: titanium at the grain boundaries and over-aging. Up to the aging time corresponding to the maximum tensile strength, the intergranular fracture strength was roughly inversely proportional to the titanium level at the grain boundaries, and after the time the tensile strength decreased with restoring ductility. Nickel or cobalt was not effective on the grain boundary strengthening of the iron-based alloys.     

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.     

EFFECT OF GRAIN BOUNDARY CARBIDE ON CREEP CRACK GROWTH IN Fe-Cr15-Ni25 ALLOY

Creep crack growth behavior of Fe-Cr15-Ni25 alloys with different grain boundary featureshas been studied.Cavities nucleate at triple junctions of grain boundaries for the single phasealloy and at grain boundary carbide for the alloy with grain boundary carbide.Grain bounda-ry carbide particles are obstacles to cavity growth and coalescence,and therefore increase thecreep crack growth resistance greatly.     

EFFECT OF HEAT TREATMENT ON INTERNAL FRICTION OF GRAIN BOUNDARY IN 2091 Al-Li ALLOY

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共析分解

对以钢中珠光体相变为典型示例的共析分解研究工作给以浅简总结。在珠光体相变中,进行铁素体和渗碳体的合作形核和长大。珠光体相变时的领先形核相,铁素体或渗碳体,及其形核位置,晶界或晶粒内部,都决定于合金的成分、晶界偏聚、夹杂物、组元的扩散系数及形核能垒。由体扩散和界面扩散两类长大机制所导得的过冷度ΔT和珠光体片层间距S之间,由Zener所示的关系式:ΔT×S=const.都与不少试验结果相符。由于珠光体/奥氏体间界面含有不动位错及其他缺陷,理论上台阶机制应为合理的珠光体长大机制。先进实验已观察到长大台阶以及铁素体/奥氏体、铁素体/渗碳体和渗碳体/奥氏体之间都具有各自的位向关系。层状珠光体的形态,即珠光体片间距受控于过冷度,并决定珠光体的强度。     

晶界碳化物对Fe-Cr15-Ni25合金蠕变裂纹扩展行为的影响SCIEI

在两种不同晶界状态下研究了Fe-Cr15-Ni25合金的蠕变裂纹扩展行为。单相合金的空洞在晶界三叉点处形核,而对晶界上有碳化物析出的合金,空洞在晶界碳化物上形核。晶界碳化物阻碍了空洞的长大和连接,因而大大提高了蠕变裂纹扩展抗力。     

Sc,La对Al-Mg焊料中杂质元素偏聚的调控作用

采用金相显微镜、扫描电镜、能谱分析和X射线衍射仪,研究了添加微量钪、镧对铝镁焊料中杂质元素偏聚的调控作用. 结果表明,在铝镁焊料合金凝固过程中,铁、硅等杂质元素在晶界有偏聚效应,添加微量钪、镧可以降低铁、硅杂质在晶界的偏聚浓度. 钪与镧减轻杂质元素在晶界偏聚的效果存在差别,添加钪的合金比添加镧的合金晶界处杂质元素偏聚强度明显减弱. 造成这种差别的原因是,钪、镧对杂质元素偏聚的调控机制不同.     

Al-Zn-Mg-Cu合金在时效过程中η相沿小角晶界的析出序列

采用高分辨透射电子显微镜和高角环形暗场扫描透射电子显微镜结合X射线能谱仪,研究Al-Zn-Mg-Cu合金叩相沿小角晶界的析出序列。试样在135℃分别时效5min到6h。结果表明,η相在小角晶界的析出序列是：SSS→VRC→GPⅡ区→η’→η。基于非平衡晶界偏析和非平衡晶界共偏析理论,在Al-Zn-Mg-Cu合金时效过程中,通过溶质一空位对的扩散,大量的沉淀形成元素偏析到晶界。这种晶界偏析在VRC、GPⅡ区、η’相和η相的形核和生长中起重要作用。