Influence of vanadium on grain boundary segregation of phosphorus in iron and iron-carbon alloys

The influence of vanadium on grain boundary segregation of phosphorus has been studied in iron and iron-carbon alloys by means of fracture experiments in a scanning Auger microprobe. The emphasis here is to study the effects of vanadium on the interaction processes operative under circumstances when structure in the interior of the grain (in the present case carbide formation) and grain boundary segregation form simultaneously. It is emphasized that to predict and analyse the behaviour of an alloy, it is important to consider atomic interactions both at the grain boundaries and in the grain interior and that between the constituents and the grain boundaries. The study suggests that the principal determining factor in the scavenging or retardation of migration of phosphorus to the grain boundaries is whether vanadium is present in the combined form (say, carbide) or is available in solid solution form. When vanadium is present in solid solution form, grain boundary segregation of phosphorus is low because of the chemical interaction of vanadium and phosphorus. However, as carbon is increasingly introduced in the alloy, vanadium now preferentially reacts with carbon in view of higher interaction for carbon as compared to phosphorus. A consequence of this is the increase in the grain boundary concentration of phosphorus. In such a situation the presence of excess carbon in addition to what is stoichiometrically required to precipitate the entire vanadium as vanadium carbides, serves as a palliative with regard to the reduction in the intergranular concentration of phosphorus. This palliative behaviour is explained in terms of the sitecompetition model. An effort is also made to examine the behaviour of segregating elements in terms of whole range of probable interactions (both at the grain boundaries and in the grain interior) and chemical interaction energies.     

Effect of solute interaction on interfacial segregation and grain boundary embrittlement in binary alloys

The effect of solute interaction on interfacial segregation and intergranular embrittlement is modeled on the basis of the combined Fowler and Rice–Wang approaches in a binary system using the chosen values of standard thermodynamic parameters of interfacial segregation and varied values of the binary interaction coefficients. It is clearly shown that attractive interaction strengthens interfacial segregation and substantially enhances intergranular embrittlement, while repulsive interaction exhibits an opposite effect. This finding is demonstrated in the available literature data.     

Grain boundary segregation produced by grain boundary movement

Experimental evidence of grain boundary enrichment is given in a temperature region where the bulk diffusion is negligible. The phenomenon can be explained by supposing that the grain boundaries gather the dissolved atoms while passing through the grains. This model can account for the enrichment on the surface of grains found by AES and for the decrease of dissolved impurities.     

Non-equilibrium segregation of solutes to grain boundary

Mechanisms for the non-equilibrium segregation of solutes to static grain boundary during cooling (quenching-induced segregation) and to moving grain boundary during recrystallization (moving-induced segregation) are proposed. For quenching-induced segregation, in consideration of the local equilibrium among vacancies, solute atoms and vacancy-solute atom complexes, as well as the influence of equilibrium grain-boundary segregation, the theoretical dynamic formulae for this non-equilibrium segregation have been derived on the basis of the vacancy-dragging mechanism. Theoretical calculations have been carried out for the non-equilibrium segregation of boron to austenitic grain boundaries during isothermal holding and continuous cooling after heating at high temperature; the results agree well with those obtained from experiments. The model has also successfully explained the different behaviours of boron segregation during cooling in -Fe and in -Fe. For moving-induced segregation, based on the interaction between dislocations and the moving boundaries during recrystallization, a dislocation relaxation and widening grain-boundary mechanism of solute segregation on moving boundaries is proposed. Applying this model, we have calculated the boron segregation on moving boundaries during recrystallization in Fe-3% Si alloy; the results of these calculations agree with experimental results.     

Non-equilibrium segregation of solute to grain boundary

The behaviour of boron segregation to grain boundaries in Fe-3%Si has been studied by means of particle tracking autoradiography. The results indicate that (i) the binding energy between boron atoms and grain boundaries is 55.7±1.7 kJ mol^–1; (ii) in contrast to the nature of boron segregation in -Fe, no observable non-equilibrium segregation of boron to grain boundaries exists in Fe-3%Si alloy during cooling and isothermal holding.     

Universal features of grain boundary networks in FCC materials

Grain boundary character distributions and triple junction distributions have been determined for 70 experimental microstructures, comprising aluminum-, copper-, austenitic iron- and nickel-based alloys in a wide variety of processed states. In these FCC metals, the fraction of coincidence site lattice (CSL) boundaries ranges from about 12% (as for a random Mackenzie distribution) to values as high as 75%. Despite wide variations in composition, processing, and grain size, we find that the grain boundary character distribution and triple junction distributions of these materials have striking similarities, and can be described by just a few parameters. This universality arises due to the highly non-random laws that govern the assembly of the grain boundary network, and due to the kinematic limitation that CSL boundaries arise primarily through twinning.     

Interactive grain boundary segregation of nickel and antimony in iron

Abstract

A study of the grain boundary segregation of nickel and antimony in iron is reported in the present paper. It is shown by the results that antimony segregation increases as the bulk nickel and antimony concentrations increase. However, once the solubility limit for antimony in iron is exceeded, the amount of segregation remains essentially constant. Segregation of nickel in iron increases as the bulk concentration of nickel increases and as the bulk concentration of antimony increases. The last effect is observed only when a certain level of antimony is reached, a level that depends on the concentration of nickel. Small additions of antimony, even though they cause an increase in segregation of antimony, do not cause an increase in segregation of nickel and, once the solubility limit for nickel in Fe–Sb alloys is exceeded, the segregation of nickel reaches a plateau. It is only between these two regimes that segregation of nickel is affected by changes in the concentration of antimony. All these results can be explained based on the mutual effects that nickel and antimony have on the solubility of each in iron. The results are not consistent with models based on cosegregation. Finally, other data in the literature are examined; all these data can be explained by an argument based on solubility changes.

MST/795     

Kinetics of grain boundary segregation during recrystallisation annealing

Abstract

In batch annealing and continuous annealing processes, both recrystallisation and grain boundary segregation can occur. In this paper, a simple model is derived which explores the interaction of the boundary migration and segregation processes and considers the application to phosphorus segregation during the annealing of interstitial free steels. The model considers both segregation to a migrating boundary and the segregation which occurs during continuous cooling after the holding period during the anneal cycle.     

A new computer model of grain boundary segregation

Improvements have been made to an earlier model of grain boundary segregation. The new model includes an influx of vacancies into the region of the material considered by the model, and accounts for the effect of a grain boundary on defect-binding energies. The model predictions for boron segregation in steel are compared with the original model.     

A new model for radiation-induced grain boundary segregation with grain boundary movement in concentrated alloy system

We have developed a new model for radiation-induced grain boundary migration (RIGM) and radiation-induced segregation (RIS) for austenitic iron-chromium-nickel alloy system. It was assumed that the RIS was induced by diffusional and annihilation processes of excess point defects at the grain boundary, and the RIGM occurred due to rearrangement process of atoms on one of the interfacial planes by annihilation of point defects. The calculated results indicated that the region of RIS was enlarged by the RIGM and asymmetrical concentration profiles were observed around the migrated grain boundary. The present model could explain the RIS behavior with or without grain boundary migration as comparing with our previous experimental results.     

Relation of ductile-to-brittle transition temperature to phosphorus grain boundary segregation for a Ti-stabilized interstitial free steel

Equilibrium grain boundary segregation of phosphorus in a Ti-stabilized interstitial free (IF) steel is measured using Auger electron spectroscopy (AES) after the specimens are aged for adequate time at different temperatures between 600 and 850 °C. Based on the experimental data of equilibrium grain boundary segregation along with the McLean equilibrium segregation theory, the free energy of segregation of phosphorus is evaluated to be ∼44.8 kJ/mol, being independent of temperature. With the AES results being combined with the ductile-to-brittle transition temperatures (DBTTs) determined by impact tests, a relationship between DBTT and phosphorus boundary concentration is established. Predictions with the relationship indicate that cold work embrittlement may be severe if the steel is annealed at relatively low temperatures after cold rolling.     

The segregation of osmium to grain boundary dislocations in tungsten

Field ion atom probe data is presented which shows that trace amounts of nickel and osmium segregate to grain boundaries in tungsten. The nickel atoms are randomly distributed in the grain boundary plane whereas the osmium is strongly segregated to the core region of a grain boundary dislocation. The differences in behavior of the solute atoms is explained by comparing atomic volumes.     

冷变形对IF钢晶界特征分布及连通性的影响

为了研究冷轧工艺对IF钢显微组织的影响.本文借助电子背散射衍射技术,研究了20%到75%冷轧压下率的IF钢退火后的微观结构、晶界特征分布和晶界连通性.结果表明:随着冷轧压下率的增加,冷轧态晶粒逐渐由等轴状变为纤维状,退火态晶粒逐渐细化并变得均匀,小角晶界的出现频率呈下降趋势;随机晶界的出现频率呈明显上升趋势,且随机晶界占绝对优势;而CSL晶界在冷轧压下率40%以下时,变化较小,40%以上时,含量明显增加.大变形量轧制后的IF钢CSL晶界主要由Σ3晶界组成,而小变形量轧制后主要是Σ3和Σ13b晶界.对于75%压下率,还含有较多的Σ7,Σ9和Σ11等CSL晶界.通过增加冷轧压下率,0-CSL三叉晶界的含量减少,1-CSL三叉晶界的含量增加.因此,通过改变冷轧工艺,可以优化IF钢板的晶界特征分布及连通性.     

Atom probe study of grain boundary segregation in technically pure molybdenum

Molybdenum, a metal with excellent physical, chemical and high-temperature properties, is an interesting material for applications in lighting-technology, high performance electronics, high temperature furnace construction and coating technology. However, its applicability as a structural material is limited because of the poor oxidation resistance at high temperatures and a brittle-to-ductile transition around room temperature, which is influenced by the grain size and the content of interstitial impurities at the grain boundaries. Due to the progress of the powder metallurgical production during the last decades, the amount of impurities in the current quality of molybdenum has become so small that surface sensitive techniques are not applicable anymore. Therefore, the atom probe, which allows the detection of small amounts of impurities as well as their location, seems to be a more suitable technique. However, a site-specific specimen preparation procedure for grain boundaries in refractory metals with a dual focused ion beam/scanning electron microscope is still required.The present investigation describes the development and successful application of such a site-specific preparation technique for grain boundaries in molybdenum, which is significantly improved by a combination with transmission electron microscopy. This complimentary technique helps to improve the visibility of grain boundaries during the last preparation steps and to evidence the presence of grain and subgrain boundaries without segregants in atom probe specimens. Furthermore, in industrially processed and recrystallized molybdenum sheets grain boundary segregation of oxygen, nitrogen and potassium is successfully detected close to segregated regions which are believed to be former sinter pores.