Dynamic process of trace boron non-equilibrium grain boundary segregation and the effect of cooling rate

The dynamic process of non-equilibrium grain boundary segregation of traceboron in Fe-40 percent Ni alloy during cooling and the effect of cooling rate were investigated byboron tracking autoradiography technique. The results indicate that during cooling process, theamount of segregated boron on grain boundary firstly increases fast, then enters a comparativelyeven increasing stage and increases rapidly again at the third stage. The details of each stagevaried with cooling rate are explained. When the segregation develops to a certain degree, thesegregated boron atoms transform from solute status to precipitate status.

NON-EQUILIBRIUM SOLUTE SEGREGATION TO AUSTENITIC GRAIN BOUNDARY IN FERRUM-NICKLE ALLOY

The development of non-equilibrium segregation of boron at grain boundaries in Fe-4 0%Ni alloy during continuous cooling process was experimentally observed with boron Particle Tracking Autoradiography (PTA) and Transmission Electron Microscopy (TEM,). The samples with 10ppm boron were cooled at 2℃/s to 1040, 980, 920, 860, 780 and 640℃ respectively after pre-heat treatment of 1150℃ for 15mm with a Gleeble-1500 heat simulating machine, then water quenched to room temperature. The width of segregation layer and boron depletion zone, rich factor and other parameters were measured by a special image analysis system. The experimental results of PTA show that the grain boundary segregation of boron during cooling process is a dynamic process and the development of the non-equilibrium segregation experiences three stages: first increases rapidly from 1150 to 1040℃, then gently from 1040 to 860℃, and rapidly again from 860℃ to 640℃. The width of boron depletion zone increases from about 11μm at 1040℃ to 26μm at 640℃. TEM observation shows that boron precipitates exist at grain boundaries when the samples are cooled to below 860℃. The experimental phenomena are briefly discussed.

Effect of nickel segregation on CuΣ9 grain boundary undergone shear deformations

Impurity segregation at grain boundary（GB） can significantly affect the mechanical behaviors of polycrystalline metal. The effect of nickel impurity segregated at Cu GB on the deformation mechanism relating to loading direction is comprehensively studied by atomic simulation. The atomic structures and shear responses of Cu Σ9（114） 110 and Σ9（221） 110 symmetrical tilt grain boundary with different quantities of nickel segregation are analyzed. The results show that multiple accommodative evolutions involving GB gliding, GB shear-coupling migration, and dislocation gliding can be at play, where for the 2ˉ21ˉ shear of Σ9（114） 110 the segregated GBs tend to maintain their initial configurations and a segregated GB with a higher impurity concentration is more inclined to be a dislocation emission source while maintaining the high mechanical strength undergone plastic deformation for the 11ˉ4ˉ shear of Σ9（221） 110. It is found that the nickel segregated GB exerts a cohesion enhancement effect on Cu under deformation： strong nickel segregation increases the work of separation of GB, which is proved by the first-principles calculations.

PSEUDO-MOLECULAR DYNAMICS STUDY 0F GRAIN BOUNDARY SEGREGATION

The segregation of bismuth atoms on the [101] tilt copper grain boundaries Σ3 (111) 70.53°, Σ33 (545) 58.99°, Σ11(323) 50.48° and Σ9 (212) 38.94° has been studied by pseudo-molecular dynamics using the empirical N-body potentials. The relationship between bismuth segregation and grain boundary structure has been discussed in detail.

ANTIMONY GRAIN BOUNDARY SEGREGATION AND ITS SUPPRESSION BY CERIUM IN Fe-2%Mn-Sb STRUCTURAL STEELS

Antimony grain boundary segregation in Fe-2%Mn-Sb structure steels has been studied through measurements of the ductile-brittle transition temperature in conjunction with scanning electron microscopy, Auger electron spectroscopy and secondary ion mass spectroscopy. The research result reveals that during tempering or ageing after quenching at 980℃, Sb segregates to grain boundaries with both equilibrium and non-equilibrium natures and brings about temper embrittlement in the steels. Cerium can relieve temper embrittlement of the steels and its segregation to grain boundaries may play an important role in reducing this embrittlement.

An FEGSTEM Study of Grain Boundary Segregation of Phosphorus during Quenching in a 2.25Cr-1Mo Steel

Quenching-induced phosphorus segregation to prior austenite grain boundaries in a 0.077 wt pct P-doped 2.25Cr-2Mo steel is examined using field emission gun scanning transmission electron microscopy （FEGSTEM）. A phosphorus level of around 1.56 at. pct is observed for the water-quenched sample. In recognition of insufficiently high spatial resolution of the technique for grain boundary composition analysis, the measured results are corrected by an analytical convolution method. The corrected phosphorus segregation level may be up to about 4.7 at. pct. The quenchinginduced phosphorus segregation is nonequilibrium segregation and the migration of vacancy-phosphorus complexes plays an important role in the kinetic process. For such a reason, the mechanism for migration of the complexes is discussed in some detail.

Modelling of Equilibrium Grain Boundary Solute Segregation under Irradiation

Both radiation-induced excess vacancies and solute-interstitials may enhance solute diffusion. The radiation-enhanced solute diffusion promotes the kinetic process of equilibrium segregation. This effect is especially considerable in the low temperature range. As a complement to modelling of radiation-induced non-equilibrium segregation, the radiation-created vacancy and solute-interstitial-accelerated equilibrium grain boundary solute segregation were theoretically treated. The models were applied to phosphorus segregation in α-Fe subjected to neutron irradiation.

BEHAVIOUR OF BORON SEGREGATION AT GRAIN BOUNDARIES IN BCC Fe-3% Si ALLOY

The behaviour of baron segregation at grain boundaries in Fe-3% Si has been studied by means of particle tracking autoradiography(PTA).The results indicate that the tendency of equilibrium segregation of B at grain boundaries in Fe-3% Si is higher than that in austenitic alloys.No observable nonequilibrium segregation of B at grain boundaries was revealed in Fe-3% Si alloy during cooling and isothermal holding.The binding energy between boron at- oms and grain boundaries is 55.7±1.7 kJ/mol.Based on the complex mechanism of B segre- gation of quenching-induce-nonequilibrium segregation,different behaviours of B segrega- tion in γ-Fe and bcc Fe-3% Si alloy were discussed.

Direct characterization of boron segregation at random and twin grain boundaries

Boron distribution at grain boundaries in hot-deformed nickel is directly characterized by the time-of-flight secondary ion mass spectrometry. The segregations of boron are observed at both the random and twin grain boundaries. Two types of segregations at random grain boundaries are observed. The first type of segregation has a high intensity and small width. Its formation is attributed to the incorporating of dislocations into the moving grain boundaries. The second type of segregation arises from the cooling induced segregation at the dislocations associated with the grain boundaries. The segregation at twin boundary is similar to the second type of segregation at random grain boundaries.

PHOSPHORUS GRAIN BOUNDARY SEGREGATION IN A P-DOPED 2.25Cr1Mo STEEL

Grain boundary segregation of phosphorus during tempering at 540℃ after quenching from 980℃ is examined for a P-doped 2.25Cr1Mo steel by means of Auger electron spectroscopy. The solute-boundary binding energy and the diffusion coefficient for phosphorus are determined by virtue of the measured segregation kinetics along with the equilibrium segregation theory. The obtained values of the above parameters are discussed with comparison to those found in the literature for low-alloy steels.

Effect of Pre-deformation on Abnormal Segregation of Grain Boundary during Recrystallization Process

The softening rates of Fe-30%Ni alloy containing boron after 10% and 40% deformation at 1000℃ have been measured by a method of interrupted compression, the recrystallization process has also been evaluated.The moving velocity of the boundary of new recrystallizing grain which was growing into the deformed grans has been calculated semi-quantitatively. By means of PTA technique, the abnormal segregation phenomenon on the moving boundary during recrystallization and the influence of pre-deformation have been investigated and the amount of B segregation on moving grain boundaries has been measured .Results indicate that the abnormal segregation of boundaries, when the new grains are growing, is concemed with the pre-deformation and the moving velocity of the bourdaries. This phenomenon is discussed by the gtain boundary widening mechanism.

Effects of Phosphorus Grain Boundary Segregation and Hardness on the Ductile-to-Brittle Transition for a 2.25CrMo Steel

The combined effect of phosphorus grain boundary segregation and hardness on the ductile-to-brittle transition was examined for a P-doped 2.25CrlMo steel by using Auger electron spectroscopy in conjunction with hardness measurements, Charpy impact tests and scanning electron microscopy. With prolonging time at 540 ~C after water quenching from 980℃, the segregation of phosphorus increases and the hardness decreases. The DBTT （FATT） increases with increasing phosphorus segregation and decreases with decreasing hardness. The effect of phosphorus segregation is dominant until 100 h aging and after that the hardness effect becomes dominant. This effect makes the DBTT （FATT） decrease with further prolonging ageing time although the segregation of phosphorus still increases strongly.

Grain boundary segregation of minor arsenic and nitrogen at elevated temperatures in a microalloyed steel

Auger electron spectroscopy （AES） was used to investigate the grain boundary segregation of arsenic and nitrogen in a kind of microalloyed steel produced by a compact strip production （CSP） technology at 950 to 1100℃, which are similar to the hot working temperature of the steel on a CSP production line. It was discovered that arsenic segregated on grain boundaries when the steel was annealed at 950℃ for 2 h. When the annealing temperature increased to 1100℃, arsenic was also found to have segregated on grain boundaries in the early annealing stage, for instance, within the first 5 min annealing time. However, if the holding time of the steel at this temperature increased to 2 h, arsenic diffused away from grain boundaries into the matrix again. Nitrogen was not found to have segregated on grain boundaries when the steel was annealed at a relatively low temperature, such as 950℃. But when the annealing temperature increased to 1100℃, nitrogen was detected to have segregated at grain boundaries in the steel.

Effects of low-frequency magnetic field on grain boundary segregation in horizontal direct chill casting of 2024 aluminum alloy

Effects of low frequency electromagnetic field on grain boundary segregation in horizontal direct chill (HDC) casting process was investigated experimentally. The grain boundary segregation and microstructures of the ingots, which manufactured by conventional HDC casting and low frequency electromagnetic HDC casting were compared. Results show that low frequency electromagnetic field significantly refines the microstructures and reduces grain boundary segregation. Decreasing electromagnetic frequency or increasing electromagnetic intensity has great effects in reducing grain boundary segregation. Meanwhile, the governing mechanisms were discussed.

Towards designing high mechanical performance low-alloyed wrought magnesium alloys via grain boundary segregation strategy:A review

Low-alloyed magnesium(Mg)alloys have emerged as one of the most promising candidates for lightweight materials.However,their further application potential has been hampered by limitations such as low strength,poor plasticity at room temperature,and unsatisfactory formability.To address these challenges,grain refinement and grain structure control have been identified as crucial factors to achieving high performance in low-alloyed Mg alloys.An effective way for regulating grain structure is through grain boundary(GB)segregation.This review presents a comprehensive summary of the distribution criteria of segregated atoms and the effects of solute segregation on grain size and growth in Mg alloys.The analysis encompasses both single element segregation and multi-element co-segregation behavior,considering coherent interfaces and incoherent interfaces.Furthermore,we introduce the high mechanical performance low-alloyed wrought Mg alloys that utilize GB segregation and analyze the potential impact mechanisms through which GB segregation influences materials properties.Drawing upon these studies,we propose strategies for the design of high mechanical performance Mg alloys with desirable properties,including high strength,excellent ductility,and good formability,achieved through the implementation of GB segregation.The findings of this review contribute to advancing the understanding of grain boundary engineering in Mg alloys and provide valuable insights for future alloy design and optimization.

Segregation of alloying atoms at a tilt symmetric grain boundary in tungsten and their strengthening and embrittling effects

We investigate the segregation behavior of alloying atoms （Sr, Th, In, Cd, Ag, Sc, Au, Zn, Cu, Mn, Cr, and Ti） near Z3 （ 111 ） [1]-0] tilt symmetric grain boundary （GB） in tungsten and their effects on the intergranular embrittlement by performing first-principles calculations. The calculated segregation energies suggest that Ag, Au, Cd, In, Sc, Sr, Th, and Ti prefer to occupy the site in the mirror plane of the GB, while Cu, Cr, Mn, and Zn intend to locate at the first layer nearby the GB core. The calculated strengthening energies predict Sr, Th, In, Cd, Ag, Sc, Au, Ti, and Zn act as embrittlers while Cu, Cr, and Mn act as cohesion enhancers. The correlation of the alloying atom＇s metal radius with strengthening energy is strong enough to predict the strengthening and embrittling behavior of alloying atoms; that is, the alloying atom with larger metal radius than W acts as an embrittler and the one with smaller metal radius acts as a cohesion enhancer.

The electronic structure and grain boundary segregation by boron addition——A binding energy shifting criterion for the brittle-ductile fracture transition in Ni_3Al

The electronic structure and grain boundary segregation caused by boron addition to Ni3Al have been studied by X-ray photoelectron spectroscopy and Auger electron spectroscopy, respectively. The obtained results show that the Ni2p3/2 electron binding energy rises gradually in the sequence of pure Ni【 Ni76Al24【 Ni74Al26 【 Ni25Al25, while it reduces monotonously with an increase in boron addition to Ni3Al. Besides, it is found that the gram boundary segregation of boron occurring in Ni3Al is a combined equilibrium and non-equilibrium type in nature. Based on the concept of the bonding environmental inhomogeneity, measured by the shift in Ni2p3/2 electron binding energy from the nickel atoms in the simple substance nickel to those in the intermetallic compound Ni3Al (ΔEB), being responsible for the brittle behavior of the alloy, a binding energy shifting criterion for the brittle-ductile fracture transition in Ni3Al is presented: when ΔEB】0, the brittle failure occurs in Ni3Al; when ΔEB【0, the ductile

Insights into grain boundary segregation and solubility limit of Cr in(TiZrNbTaCr)C

Dense(TiZrNbTaCr)C with Cr segregation along grain boundaries(GBs)has been first proposed and fabri-cated by pressureless sintering at 1800-2000℃,utilizing the self-synthesized carbide powders obtained by carbothermal reduction.Cr segregation along GBs is successfully realized as expected via optimizing the initial Cr content.When Cr content is more than 11.12 at.%,Cr addition is excessive and results in Cr-rich second phase formation at triple junctions.To analyze the Cr solubility dependence on tempera-ture and initial Cr content,the Cr content in(TiZrNbTaCr)C grains is investigated by EDS.The solubility limit of Cr in(TiZrNbTaCr)C is about 3.8 at.%at 1900℃.Finally,Vickers hardness of all the samples is measured to assess the mechanical property of(TiZrNbTaCr)C ceramics.The basic understanding of the Cr solubility limit and GB segregation feature in(TiZrNbTaCr)C have been preliminarily clarified,which may pave a potential way to design and tailor microstructure and GB feature of(TiZrNbTaCr)C for the purpose of enhancing its properties in the future.

Segregation behavior and embrittling effect of lanthanide La, Ce, Pr,and Nd at Σ3(111) tilt symmetric grain boundary in α-Fe

The migration of lanthanide fission products to cladding materials is recognized as one of the key causes of fuel–cladding chemical interaction(FCCI) in metallic fuels during operation. We have performed first-principles density functional theory calculations to investigate the segregation behavior of lanthanide fission products(La, Ce, Pr, and Nd) and their effects on the intergranular embrittlement at Σ3(111) tilt symmetric grain boundary(GB) in α-Fe. It is found that La and Ce atoms tend to reside at the first layer near the GB with segregation energies of-2.55 eV and-1.60 eV, respectively,while Pr and Nd atoms prefer to the core mirror plane of the GB with respective segregation energies of-1.41 eV and-1.50 eV. Our calculations also show that La, Ce, Pr, and Nd atoms all act as strong embrittlers with positive strengthening energies of 2.05 eV, 1.52 eV, 1.50 eV, and 1.64 eV, respectively, when located at their most stable sites. The embrittlement capability of four lanthanide elements can be determined by the atomic size and their magnetism characters. The present calculations are helpful for understanding the behavior of fission products La, Ce, Pr, and Nd in α-Fe.

Role of grain boundary character on Bi segregation-induced embrittlement in ultrahigh-purity copper

Bismuth(Bi),as an impurity element in copper and copper-based alloys,usually has a strong tendency of grain boundary(GB)segregation,which depends on the GB characters.However,the influence of such a segregation on the properties of ultrahigh-purity copper has been rarely reported and the exact structural arrangements of Bi atoms at different GBs remain largely unclear.In this study,we investigated the influ-ence of trace amounts of Bi(50-300 wt ppm)on the ductility of an ultrahigh-purity copper(99.99999%)in the range of room temperature to 900°C.The tensile results show that the addition of Bi seriously damages the ductility of the ultrahigh-purity copper at temperatures of 450-900°C,which is due to the GB segregation of Bi.On this basis,such a segregation behavior at different types of GBs,including high and low angle GBs(HAGBs/LAGBs),and twin boundaries(TBs),via the scanning electron microscope-electron backscattered diffraction(SEM-EBSD)and aberration-corrected scanning transmission electron microscope(AC-STEM)investigations,combined with the first-principles calculations were systematically studied.The atomistic characterizations demonstrate an anisotropic Bi segregation,where severe enrich-ment of Bi atoms typically occurs at the HAGBs,while the absence of Bi adsorption prevails at LAGBs or TBs.In particular,the segregated Bi at random HAGBs exhibited the directional bilayer adsorption,while the special symmetrical7 HAGB presented a unique Bi-rich cluster superstructure.Our findings pro-vide a comprehensive experimental and computational understanding on the atomic-scale segregation of impurities in metallic materials.