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.

Non-equilibrium grain-boundary segregation of Bi in Cu bicrystals

The observations of grain-boundary segregation of Bi in Cu bicrystals were analyzed. According to equilibrium grain boundary segregation （EGS） model and non-equilibrium grain-boundary segregation （NGS） model, respectively, the segregation kinetics of isothermal annealing at 500 ＆#176;C and that of isochronal annealing for 24 h of Bi in Cu bicrystals were investigated. By qualitative analysis and quantitative analysis, it is concluded that the grain-boundary segregation of Bi agrees well with the theory of NGS. Based on the kinetics model of NGS, some parameters that are useful to predicting and controlling the Bi-induced embrittlement in Cu alloys are calculated as follows：the diffusion coefficient of Bi-vacancy complexes Dc=7.8×10^-5exp[-1.46/（kT）];the apparent diffusion coefficient of Bi atoms Di^A=7.66×10^at＋bexp[–1.76/（kT）], where a=8.45×10^-8 and b=-13.37.

COMPUTER SIMULATION OF GRAIN BOUNDARY SEGREGATION BEHAVIOR AND MECHANISMS OF STRENGTHENING OF Mg IN Ni-BASED SUPERALLOYS

This paper used EAM and static relaxation method to simulate the grain boundary segregation behavior of Mg in Ni-based superalloys. The results offer a better understanding in the strengthening mechanism of Mg addition in superalloys. The segregation of Mg increases the grain boundary cohesive bond and the vacancy formation energy, and decreases the mobility of grain boundary dislocation. It results in the retardation of creep voids initiation and growth.

GRAIN BOUNDARY SEGREGATION AND INTERGRANULAR BRITTLENESS IN HIGH STRENGTH ALUMINIUM ALLOY

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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.

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.

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.

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.

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.

Determination of Neutron Irradiation-Induced Phosphorus Segregation on Grain Boundaries in a P-doped 2.25Cr1Mo Steel

Irradiation-induced impurity segregation to grain boundaries is one of the important radiation effects on materials. For this reason, phosphorus segregation to prior austenite grain boundaries in a P-doped 2.25Cr1Mo steel subjected to neutron irradiation is examined using field emission gun scanning transmission electron microscopy (FEGSTEM) with energy dispersive X-ray microanalysis (EDX). The steel samples are irradiated around 270 and 400℃, respectively. The irradiation dose rate and dose are -1.05×10-8 dpa/s and -0.042 dpa respectively for 270℃ irradiation, and 1.7×10-8 dpa/s and 0.13 dpa respectively for 400℃ irradiation. The FEGSTEM results indicate that there is no apparent phosphorus segregation during 270℃ irradiation but there is some during 400℃ irradiation.

The Role of Nd Solid-Solution and Grain-Boundary Segregation in Binary NiAl Intermetallic Compound

The role of Nd solid-solution and grain-boundary segregation in binary NiAl alloy was studied based on microhardness and compressive macrostrain. X-ray and Auger spectra studies indicate that Nd not only is soluble in grain interiors, but also segregates to the grain boundaries. Nd solid-solution induces an increase of the microhardness from 269 to 290 HV in grain interiors and segregation results in an enhancement of hardness from 252 to 342 HV on grain boundaries. Thus, the cohesion of grain boundaries is enhanced by Nd segregation, which make the alloy doped with 0.05 wt pct Nd exhibit more compressive microstrain, i.e. the higher the compressive ductility at room temperature, the better the final surface condition at elevated temperature. Finally, a discussion was made on the reason that Nd strengthens the grain boundaries in NiAl intermetallic alloy.

From protonation & Li-rich contamination to grain-boundary segregation: Evaluations of solvent-free vs. wet routes on preparing Li_(7)La_(3)Zr_(2)O_(12) solid electrolyte

Garnet-type Li_(7)La_(3)Zr_(2)O_(12)(LLZO) has been recognized as a candidate solid electrolyte for high-safety Lianode based solid-state batteries because of its electro-chemical stability against Li-metal and high ionic conductivity. Solvent(e.g., isopropanol(IPA)) has been commonly applied for preparing LLZO powders and ceramics. However, the deterioration of the proton-exchange between LLZO and IPA/absorbed moisture during the mixing and tailoring route has aroused less attention. In this study, a solvent-free dry milling route was developed for preparing the LLZO powders and ceramics. For orthogonal four categories of samples prepared using solvent-free and IPA-assisted routes in the mixing and tailoring processes, the critical evaluation was conducted on the crystallinity, surficial morphology, and contamination of ascalcinated and as-tailored particles, the cross-sectional microstructure of green and sintered pellets,the morphology and electro-chemical properties of grain boundaries in ceramics, as well as the interfacial resistance and performance of Li anode based symmetric batteries. The wet route introduced Li-rich contaminations(e.g., Li OH·H)_(2)O and Li)_(2)CO)_(3)) onto the surfaces of LLZO particles and Li-Ta-O segregations at the adjacent and triangular grain boundaries. The LLZO solid electrolytes prepared through dry mixing in combination with the dry tailoring route without the use of any solvent were found to the optimal performance. The fundamental material properties in the whole LLZO preparation process were found, which are of guiding significance to the development of LLZO powder and ceramic production craft.

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.

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.

NON-EQUILIBRIUM SEGREGATION OF SOLUTE TO GRAIN BOUNDARIES

In consideration of the local equilibrium among vacancies,solute atoms and vacancy-solute atom complexes and the influence of equilibrium grain boundary segregation,theoretical dy- namic formulas for non-equilibrium grain boundary segregation of solute have been derived on the basis of the vacancy-dragging mechanism.Theoretical calculation by computer has been carried out for the non-equilibrium segregation of boron to austenitic grain boundaries during isothermal holding and continuous cooling after heating at high temperatures.The re- suits agree well with those obtained from experiments.

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.

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.

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.

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.