Electronic Theoretical Study of the Interaction between Rare Earth Elements and Impurities at Grain Boundaries in Steel

Rareearths(RE)aresurfaceactiveelements ,theirapplicationsinmetalmaterialscanbesum marizedaspurification ,modificationandall oying[1～ 3 ] .Itisaveryattractivesubjectthattheinter actionofREelementswithlowmeltingpointimpuri tiesintheregionofGBs ,suchasP ,S ,As ,Sbandsoon .ResultsofexperimentsshowthatsegregationinGBsofasmallamountofREinsteelrestrainsharmfulimpuritiessuchasP ,S ,As ,Pb ,Sb ,tosegregateto wardsGBs ,soREelementscancleanseandenhanceGBs ,therebyimprovethehightemperatureducti…     

The Influence of Alloying Elements on Impurity Induced Grain Boundary Embrittlement

A nonequilibrium thermodynamic model which describes the effect of solute grain boundary segregation on grain boundary cohesion was extended to Fe ternary systems. The extended model directly and simply predicts the effect of alloying elements on impurity-induced grain boundary embrittlement. According to the extended model, Mo, W, and Zr strongly reduce, Ni, Ti, and V slightly reduce, and Cr and Mn enhance impurity-induced grain boundary embrittlement in an Fe ternary system. For the evaluation of the extended model, Fe-P, Fe-P-Mn, Fe-P-Mo, and Fe-P-W alloys were studied by Auger electron spectroscopy, scanning electron microscopy, 4-point slow bend tests, and tension tests. The experimental results show that for a given amount of P grain boundary segregation the grain boundary strength increases with increasing Mo or W grain boundary segregation and decreases with increasing Mn grain boundary segregation. These experimental results showing the remedial effect of Mo or W and the embrittling effect of Mn on P-induced grain boundary embrittlement are consistent with the predicted results from the extended model. The nonequilibrium model is also used to evaluate impurity-induced interfacial embrittlement in continuous fiber metal matrix composite materials.     

A first-principles study on electronic structures and elastic properties of metal dopedα-Fe(N) high nitrogen steel

The binding energies,electronic structures and elastic properties of Ti,V,Cr,Mn,Co,Ni and Mg dopedα-Fe(N)systems have been investigated using a first-principles method.The calculated results show that the dopings of Ti,V,Cr and Co improve the stability ofα-Fe(N),and the stability ofα-Fe(N)is slightly weakened by Mn and Ni,and the doping of Mg is disadvantageous.For Ti,V,Cr and Mn dopedα-Fe(N)systems in which the doping metals are on the left side of Fe in the element periodic table andα-Fe(N)systems doped by Co and Ni on the right side of Fe,their corresponding cohesive forces decrease with decreasing atomic radius of the doping species.The obvious interaction exists among M3 d,Fe4s3p3d and N2 p.In these doping systems,metal atoms lose electrons,while N gains electrons.Dopings of Ti,V,Cr and Mn inα-Fe(N)strengthen the interaction between N and the surrounding metals,and it is not apparent for the dopings of Co,Ni and Mg.Elastic calculations of Fe15 MN systems show that,except for the Fe15 MgN system,shear modulus G and Young modulus E of Fe15 MN systems are improved,and the bulk modulus Bslightly decreases,namely,total elastic properties are enhanced.The magnitude change rule of E reflecting the cohesive force between atoms is consistent with that for the binding energies.     

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.     

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.     

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 influence of intercritical heat treatment on the temper embrittlement susceptibility of aP-Doped Ni-Cr steel

Temper embrittlement of a Ni-Cr steel doped with 0.06 wt pct P aged at 480°C after an intercritical heat treatment (IHT) has been compared with that of the conventionally heat treated steel with a range of prior austenite grain sizes. The IHT virtually eliminated the embrittlement susceptibility, but low temperature brittle fracture was still intergranular. It appears that most of the benefit of IHT in this steel comes from microstructural refinement; however, IHT also reduced the amount of segregation of Ni and P to grain boundaries. This is believed to be connected with partitioning of Cr during IHT. Formerly Post Doctoral Fellow, Department of Metallurgy and Materials Science, University of Pennsylvania Formerly on the Research Staff, LRSM, 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     

First-Principles Study on the Grain Boundary Embrittlement of Metals by Solute Segregation: Part I. Iron (Fe)-Solute (B,C, P,and S) Systems

The microscopic mechanism of grain boundary (GB) embrittlement in metals by solute segregation has been not well understood for many years. From first-principles calculations, we show here that the calculated cohesive energy (=2·surface energy − GB energy) of bcc Fe Σ3(111) symmetrical tilt grain boundary (STGB) is reduced by the segregation of sulfur (S) and phosphorous (P) while it is increased by the segregation of boron (B) and carbon (C). The rate of the decrease/increase in the cohesive energy is proportional to the experimental shift in the DBTT of high-purity iron with increasing segregation. This indicates that the change in the cohesive energy of GB plays a key role in the GB embrittlement of metals.     

Temper embrittlement of Ni-Cr steel by antimony: III. Effects of Ni and Cr

The individual effects of Ni and Cr on temper embrittlement in a Ni-Cr steel doped with Sb were studied by notched-bar testing and Auger electron spectroscopy. Nickel is required for significant segregation of Sb to grain boundaries (and concomitant embrittlement). The addition of Cr somehow makes Ni more effective in this respect; segregation of Cr was not detected. Precipitation of Cr-rich carbides, which depletes the α matrix of Cr, reduces the embrittlement susceptibility. The amount of segregated Ni is a function only of the amount of segregated Sb; it is independent of Cr or C content of the steel. Formerly Research Fellow at Department of Metallurgy and Materials Science, University of Pennsylvania, Philadelphia, PA 19174.     

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.     

掺杂对锂离子筛吸附性能的影响

对Li/Mn为0.7的离子筛分别进行了铜钴镍的掺杂,XRD检测和化学分析表明掺杂元素进入了离子筛的晶格;掺入铜钴镍后离子筛中锰的溶损率分别降低了2%、1.3%、1.2%;饱和吸附容量随掺入元素量的增加逐渐变小,当掺入铜钴镍的量由0增加到0.15时,饱和吸附容量由27.6 mg/g分别下降到7.8 mg/g、13.3 mg/g、18.3 mg/g。铜钴镍在离子筛中能降低锰的溶损率,但同时也降低了饱和吸附容量。     

Effect of vanadium on grain boundary segregation of phosphorus in low alloy steels

The phosphorus grain boundary segregation at 853 K was investigated in three low alloy steels with different vanadium content. Kinetic dependence of the phosphorus grain boundary concentration was determined experimentally by means of AES and described theoretically, as well. To assess the influence of the individual alloying elements on the phosphorus segregation, the metal composition of carbide phases at 853 K was predicted by means of thermodynamic calculations and confirmed by experimental measurements (TEM + EDX). The vanadium was found to enhance the phosphorus grain boundary segregation by reducing the amount of dissolved and segregated carbon. Thereby, the equilibrium of mutual displacement C (segregated) ? P (segregated) was shifted to more phosphorus segregation. The results achieved indicate that vanadium indirectly increases sensitivity of low alloy steels to intergranular embrittlement.     

BInfluence of Cerium and Phosphorus onEmbrittlement in Manganese Steels

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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 effects of alloying elements on the susceptibility to stress-corrosion cracking of martensitic steels in salt water

The effects of a number of elements (C, Mn, Cr, Mo, Ni, Co, P, and S) on the stress-corrosion cracking (SCC) resistance in salt water of some quenched-and-tempered steels were investigated. Values of the threshold stress intensity for crack growth in salt water (K _Iscc) were measured using the cantilever beam test and precracked specimens. Values of the fracture toughness parameterK _Ix (an approximation ofK _Ic) were also determined. The steels were either Fe-C alloys to which alloying elements were added, or basically of AISI 4340-type composition in which alloying elements were varied. All steels in a series to show the effects of a given element were heat treated to the same yield strength, and generally the effects of an element were determined at two yield strength levels. The results show that only carbon and manganese are definitely harmful to SCC resistance.     

Experimental Evidence of the Effect of Alloying Additions on the Stagnant Stage Length During Cyclic Partial Phase Transformations

Cyclic phase transformation experiments are performed in a series of Fe-C-xMn, Fe-C-Mn-xNi, and Fe-C-Mn-xCo alloys to study the effect of alloying elements on the length of the stagnant stage during a cyclic partial phase transformation in the austenite–ferrite two-phase region. The length of stagnant stage increases linearly with the increasing Mn or Ni concentration, while Co has no effect. It was experimentally proven that the effects of alloying elements on the length of stagnant stage are additive, and the experimental results matched the predictions of the local equilibrium model very well.     

Effect of the presence of alloying elements in interstitial-free and low-carbon steels on their surface composition after annealing in reducing atmospheres (dew point=−30 °C)

The X-ray photoelectron spectroscopy (XPS) method is used to study the outer surfaces of interstitial-free (IF) and low-carbon (LC) steels with different alloying element contents (P, Ti, Nb, and Mn) after annealing at temperatures of 805 °C and 705 °C, respectively, for 40 seconds in reducing atmospheres (dew point=−30 °C). The work discussed seeks to establish possible relationships between the bulk composition of the IF and LC steels and the contents of segregated alloying element observed by XPS on the surface of the annealed steels, as well as to establish the influence of the presence of a thin iron oxide film on the steel surface on the segregation and oxidation of the alloying elements. Despite the low Mn and Si bulk steel contents and the shortness of the annealing cycle, considerable enrichment of these elements on the surface is seen, mainly as manganese and silicon oxides. The formation of a MnO layer on the annealed steel surface seems to be related to the reduction of iron oxides and the increase in the metallic Fe content. Despite its low content in LC steels, carbon also seems to diffuse towards the annealed steel surface to reduce iron oxides.     

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.