Grain boundary engineering for enhancing intergranular damage resistance of ferritic/martensitic steel P92

Ferritic/martensitic(F/M)steel is widely used as a structural material in thermal and nuclear power plants.However,it is susceptible to intergranular damage,which is a critical issue,under service conditions.In this study,to improve the resistance to intergranular damage of F/M steel,a thermomechanical process(TMP)was employed to achieve a grain boundary engineering(GBE)microstructure in F/M steel P92.The TMP,including cold-rolling thickness reduction of 6%,9%,and 12%,followed by austenitization at 1323 K for 40 min and tempering at 1053 K for 45 min,was applied to the as-received(AR)P92 steel.The prior austenite grain(PAG)size,prior austenite grain boundary character distribution(GBCD),and connectivity of prior austenite grain boundaries(PAGBs)were investigated.Compared to the AR specimen,the PAG size did not change significantly.The fraction of coincident site lattice boundaries(CSLBs,3≤Σ≤29)and Σ3^(n) boundaries along PAGBs decreased with increasing reduction ratio because the recrystallization fraction increased with increasing reduction ratio.The PAGB connectivity of the 6%deformed specimen slightly deteriorated compared with that of the AR specimen.Moreover,potentiodynamic polarization studies revealed that the intergranular damage resistance of the studied steel could be improved by increasing the fraction of CSLBs along the PAGBs,indicating that the TMP,which involves low deformation,could enhance the intergranular damage resistance.

Modeling the Interaction between Vacancies and Grain Boundaries during Ductile Fracture

The experimental results in previous studies have indicated that during the ductile fracture of pure metals,vacancies aggregate and form voids at grain boundaries.However,the physical mechanism underlying this phenomenon remains not fully understood.This study derives the equilibrium distribution of vacancies analytically by following thermodynamics and the micromechanics of crystal defects.This derivation suggests that vacancies cluster in regions under hydrostatic compression to minimize the elastic strain energy.Subsequently,a finite element model is developed for examining more general scenarios of interaction between vacancies and grain boundaries.This model is first verified and validated through comparison with some available analytical solutions,demonstrating consistency between finite element simulation results and analytical solutions within a specified numerical accuracy.A systematic numerical study is then conducted to investigate the mechanism that might govern the micromechanical interaction between grain boundaries and the profuse vacancies typically generated during plastic deformation.The simulation results indicate that the reduction in total elastic strain energy can indeed drive vacancies toward grain boundaries,potentially facilitating void nucleation in ductile fracture.

Effects of Fe solid solute on grain boundaries of bi-crystal Cu: A molecular dynamics simulation

Grain boundaries(GBs)play a crucial role on the structural stability and mechanical properties of Cu and its alloys.In this work,molecular dynamics(MD)simulations are employed to study the effects of Fe solutes on the formation energy,excess volume,dislocations and melting behaviors of GBs in CuFe alloys.It is illustrated that Fe solute affects the structural stability of Cu GBs substantially,the formation energy of GBs is reduced,but the thickness and melting point of GBs are increased,that is,the structural stability of Cu GBs is significantly improved owing to the Fe solutes.A strong scaling law exists between the formation energy,excess volume,thickness and melting point of GBs.Therefore,Fe solid solute plays an important role in the characteristics of GBs in bi-crystal Cu.

Thermodynamics-directed bulk/grain-boundary engineering for superior electrochemical durability of Ni-rich cathode

Introducing high-valence Ta element is an essential strategy for addressing the structu ral deterioration of the Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)cathode,but the enlarged Li/Ni cation mixing leads to the inferior rate capability originating from the hindered Li~+migration.Note that the non-magnetic Ti~(4+)ion can suppress Li/Ni disorder by removing the magnetic frustration in the transition metal layer.However,it is still challenging to directionally design expected Ta/Ti dual-modification,resulting from the complexity of the elemental distribution and the uncertainty of in-situ formed coating compounds by introducing foreign elements.Herein,a LiTaO_3 grain boundary(GB)coating and bulk Ti-doping have been successfully achieved in LiNi_(0.834)Co_(0.11)Mn_(0.056)O_(2) cathode by thermodynamic guidance,in which the structural formation energy and interfacial binding energy are employed to predict the elemental diffusion discrepancy and thermodynamically stable coating compounds.Thanks to the coupling effect of strengthened structural/interfacial stability and improved Li~+diffusion kinetics by simultaneous bulk/GB engineering,the Ta/Ti-NCM cathode exhibits outstanding capacity retention,reaching 91.1%after 400 cycles at 1 C.This elaborate work contributes valuable insights into rational dual-modification engineering from a thermodynamic perspective for maximizing the electrochemical performances of NCM cathodes.

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.

Quantification of grain boundary effects on the geometrically necessary dislocation density evolution and strain hardening of polycrystalline Mg-4Al using in situ tensile testing in scanning electron microscope and HR-EBSD

In situ tensile testing in a scanning electron microscope(SEM)in conjunction with high-resolution electron backscatter diffraction(HR-EBSD)under load was used to characterize the evolution of geometrically necessary dislocation(GND)densities at individual grain boundaries as a function of applied strain in a polycrystalline Mg-4Al alloy.The increase in GND density was investigated at plastic strains of 0%,0.6%,2.2%,3.3% from the area including 76 grains and correlated with(i)geometric compatibility between slip systems across grain boundaries,and(ii)plastic incompatibility.We develop expressions for the grain boundary GND density evolution as a function of plastic strain and plastic incompatibility,from which uniaxial tensile stress-strain response of polycrystalline Mg-4Al are computed and compared with experimental measurement.The findings in this study contribute to understanding the mechanisms governing the strain hardening response of single-phase polycrystalline alloys and more reliable prediction of mechanical behaviors in diverse microstructures.

Atomistic study on the microscopic mechanism of grain boundary embrittlement induced by small dense helium bubbles in iron

The helium bubbles induced by 14 MeV neutron irradiation can cause intergranular fractures in reduced activation ferritic martensitic steel,which is a candidate structural material for fusion reactors.In order to elucidate the susceptibility of different grain boundaries(GBs)to helium-induced embrittlement,the tensile fracture processes of 10 types of GBs with and without helium bubbles in body-centered cubic(bcc)iron at the relevant service temperature of 600 K were investigated via molecular dynamics methods.The results indicate that in the absence of helium bubbles,the GBs studied here can be classified into two distinct categories:brittle GBs and ductile GBs.The atomic scale analysis shows that the plastic deformation of ductile GB at high temperatures originates from complex plastic deformation mechanisms,including the Bain/Burgers path phase transition and deformation twinning,in which the Bain path phase transition is the most dominant plastic deformation mechanism.However,the presence of helium bubbles severely inhibits the plastic deformation channels of the GBs,resulting in a significant decrease in elongation at fractures.For bubble-decorated GBs,the ultimate tensile strength increases with the increase in the misorientation angle.Interestingly,the coherent twin boundary∑3{112}was found to maintain relatively high fracture strength and maximum failure strain under the influence of helium bubbles.

Plasma induced grain boundaries to boost electrochemical reduction of CO_(2)to formate

Bismuth-based catalysts are highly promising for the electrochemical carbon dioxide reduction reaction(eCO_(2)RR)to formate product.However,achieving high activity and selectivity towards formate and ensuring long-term stability remains challenging.This work reports the oxygen plasma inducing strategy to construct the abundant grain boundaries of Bi/BiO_x on ultrathin two-dimensional Bi nanosheets.The oxygen plasma-treated Bi nanosheet(OP-Bi)exhibits over 90%Faradaic efficiency(FE)for formate at a wide potential range from-0.5 to-1.1 V,and maintains a great stability catalytic performance without significant decay over 30 h in flow cell.Moreover,membrane electrode assembly(MEA)device with OPBi as catalyst sustains the robust current density of 100 mA cm^(-2)over 50 h,maintaining a formate FE above 90%.In addition,rechargeable Zn-CO_(2)battery presents the peak power density of1.22 mW cm^(-2)with OP-Bi as bifunctional catalyst.The mechanism experiments demonstrate that the high-density grain boundaries of OP-Bi provide more exposed active sites,faster electron transfer capacity,and the stronger intrinsic activity of Bi atoms.In situ spectroscopy and theo retical calculations further elucidate that the unsaturated Bi coordination atoms between the grain boundaries can effectively activate CO_(2)molecules through elongating the C-O bond,and reducing the formation energy barrier of the key intermediate(^(*)OCOH),thereby enhancing the catalytic performance of eCO_(2)RR to formate product.

Heterogeneities of grain boundary contact for simulation of laboratoryscale mechanical behavior of granitic rocks

From a practical point of view,grain structure heterogeneities are key parameters that control the rock response and still remains a challenge to incorporate in a quantitative manner.One of the less discussed topics in the context of the grain-based model(GBM)in the particle flow code(PFC)is the contact heterogeneities and the appropriate contact model to mimic the grain boundary behavior.Generally,the smooth joint(SJ)model and linear parallel bond(LPB)model are used to simulate the grain boundary behavior.However,the literature does not document the suitability of different models for specific problems.Another challenge in implementing GBM in PFC is that only a single bonding parameter is used at the grain boundaries.The aim of this study is to investigate the responses of a laboratory-scale specimen with SJ and LPB models,considering grain boundary heterogeneous and homogeneous contact parameters.Uniaxial and biaxial compression tests are performed to calibrate the response of Creighton granite.The stressestrain curves,volumetric dilation,inter-crack(crack in the grain boundary),and intra-crack(crack within the grain)development,and failure patterns associated with different contact models are examined.It was found that both the SJ and LPB models can reproduce the pre-peak behavior observed for a granitic rock type.However,the LPB model is unable to reproduce the post-peak behavior.Due to the large interlocking effect originating from the balls in contact and the ball size in the LPB model,local dilation is induced at the grain boundaries.This overestimates the volumetric dilation and residual shear strength.The LPB model tends to result in discontinuous inter-cracks and stress localization in the rock specimen,resulting in fine fragments at the rock surface during failure.

Nano-capillary induced assemble of quantum dots on perovskite grain boundaries for efficient and stable perovskite solar cells

In recent years, perovskite solar cells(PSCs) have propelled into the limelight owing to rapid development of efficiency;however, the abundant defects at the perovskite grain boundaries result in unwanted energy loss and structural degradation. Here, the grain boundaries of perovskite polycrystalline films have been found to act as nanocapillaries for capturing perovskite quantum dots(PQDs), which enable the conformal assemble of PQDs at the top interspace between perovskite grains. The existence of PQDs passivated the surface defects, optimized the interfacial band alignments, and ultimately improved the power conversion efficiency from 19.27% to 22.47% in inverted PSCs. Our findings open up the possibility of selective assembly and structural modulation of the perovskite nanostructures towards efficient and stable PSCs.

Role of grain boundary networks in vortex motion in superconducting films

We study the vortex dynamics of the polycrystalline superconductors in the presence of both random point defects and the generated grain boundary(GB) networks with Voronoi diagram. The synergistic effect of adjacent GBs on restricting the vortex motion in intragranular region is proposed and the corresponding intensity factor of the synergistic effect which characterizes the strength of the synergistic restriction of adjacent grain boundaries is also determined in the present work.The interconnected GBs offer easy-flow channels for vortices in addition to pinning effects on the vortices. The combined channels and the vortex flow patterns in the superconducting film are analyzed in detail from molecular dynamics simulations. Furthermore, it is discovered that the critical current increases with the decrease of magnetic field intensity,temperature, and the average grain size. The large number of vortices results in the enhanced repulsive interaction forcing the vortices to move out from the GBs. The thermal depinning from GBs leads to the lower Lorentz force range. The increase of the grain size causes the number of GBs to decrease. In summary, these effects leads the critical current to become a decreasing function of magnetic field, temperature, and grain size.

Coercivity enhancement of sintered Nd–Fe–B magnets by grain boundary diffusion with Pr_(80-x)Al_(x)Cu_(20)alloys

A grain boundary diffusion(GBD)process with Pr_(80-x)Al_(x)Cu_(20)(x=0,10,15,20)low melting point alloys was applied to commercial 42M sintered Nd–Fe–B magnets.The best coercivity enhancement of a diffused magnet was for the Pr_(65)Al_(15)Cu_(20)GBD magnet,from 16.38 kOe to 22.38 kOe.Microstructural investigations indicated that increase in the Al content in the diffusion source can form a continuous grain boundary(GB)phase,optimizing the microstructure to enhance the coercivity.The coercivity enhancement is mainly due to the formation of a continuous GB phase to separate the main phase grains.Exchange decoupling between the adjacent main phase grains is enhanced after the GBD process.Meanwhile,the introduction of Al can effectively promote the infiltration of Pr into the magnet,which increases the diffusion rate of rare-earth elements within a certain range.This work provides a feasible method to enhance coercivity and reduce the use of rare-earth resources by partial replacement of rare-earth elements with non-rare-earth elements in the diffusion source.

The Influence of Crystallographic Orientation and Grain Boundary on Nanoindentation Behavior of Inconel 718 Superalloy Based on Crystal Plasticity Theory

The crystal plasticity finite element method(CPFEM)is widely used to explore the microscopic mechanical behavior of materials and understand the deformation mechanism at the grain-level.However,few CPFEM simulation studies have been carried out to analyze the nanoindentation deformation mechanism of polycrystalline materials at the microscale level.In this study,a three-dimensional CPFEM-based nanoindentation simulation is performed on an Inconel 718 polycrystalline material to examine the influence of different crystallographic parameters on nanoindentation behavior.A representative volume element model is developed to calibrate the crystal plastic constitutive parameters by comparing the stress-strain data with the experimental results.The indentation force-displacement curves,stress distributions,and pile-up patterns are obtained by CPFEM simulation.The results show that the crystallographic orientation and grain boundary have little influence on the force-displacement curves of the nanoindentation,but significantly influence the local stress distributions and shape of the pile-up patterns.As the difference in crystallographic orientation between grains increases,changes in the pile-up patterns and stress distributions caused by this effect become more significant.In addition,the simulation results reveal that the existence of grain boundaries affects the continuity of the stress distribution.The obstruction on the continuity of stress distribution increases as the grain boundary angle increases.This research demonstrates that the proposed CPFEM model can well describe the microscopic compressive deformation behaviors of Inconel 718 under nanoindentation.

Optimization of the grain boundary diffusion process by doping gallium and zirconium in Nd–Fe–B sintered magnets

As the channel for grain boundary diffusion(GBD)in Nd–Fe–B magnets,grain boundary(GB)phases have a very important effect on GBD.As doping elements that are commonly used to regulate the GB phases in Nd–Fe–B sintered magnets,the influences of Ga and Zr on GBD were investigated in this work.The results show that the Zr-doped magnet has the highest coercivity increment(7.97 kOe)by GBD,which is almost twice that of the Ga-doped magnet(4.32 kOe)and the magnet without Ga and Zr(3.24 kOe).Microstructure analysis shows that ZrB_(2)formed in the Zr-doped magnet plays a key role in increasing the diffusion depth.A continuous diffusion channel in the magnet can form because of the presence of ZrB_(2).ZrB_(2)can also increase the defect concentration in GB phases,which can facilitate GBD.Although Ga can also improve the diffusion depth,its effect is not very obvious.The micromagnetic simulation based on the experimental results also proves that the distribution of Tb in the Zr-doped magnet after GBD is beneficial to coercivity.This study reveals that the doping elements Ga and Zr in Nd–Fe–B play an important role in GBD,and could provide a new perspective for researchers to improve the effects of GBD.

Non-isothermal retrogression kinetics for grain boundary precipitate of 7A55 aluminum alloy

The retrogression kinetics for grain boundary precipitate （GBP） of 7A55 aluminum alloy was investigated by transmission electron microscopy （TEM） observation. The results reveal that the coarsening behavior of GBP obeys “LSW” theory, namely, the cube of GBP average size has a linear dependence relation to retrogression time, and the coarsening rate accelerates at the elevated retrogression temperature. The GBP coarsening activation energy Qo of （115.2±1.3） kJ/mol is obtained subsequently. Taking the retrogression treatment schedule of 190℃, 45 min derived from AA7055 thin plate as reference, the non-isothermal retrogression model for GBP coarsening behavior is established based on “LSW”theory and “iso-kinetics” solution, which includes an Arrhenius form equation. After that, the average size of GBP r（t） is predicted successfully at any non-isothermal process T（t） when the initial size of GBP r0 is given. Finally, the universal characterization method for the microstructure homogeneity along the thickness direction of TA55 aluminum alloy thick plate is also set up.

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.

Precipitation sequence of η phase along low-angle grain boundaries in Al-Zn-Mg-Cu alloy during artificial aging

The precipitation sequence of η（MgZn2） phase along low-angle grain boundaries in Al-Zn-Mg-Cu alloy was investigated by examining samples aged at 135 ℃ for various times from 5 min to 6 h. High resolution transmission electron microscopy （HRTEM） observations and energy dispersive X-ray spectroscopy （EDX） analysis indicate that the precipitation sequence of η phase along low-angle grain boundaries should be supersaturated solid solution （SSS）→vacancy-rich clusters （VRC）→GP Ⅱ zones→η＇→η. Based on the theory of non-equilibrium grain boundary segregation （NGS） and non-equilibrium grain boundary co-segregation （NGCS）, the excessive solute elements gradually segregate to the grain boundaries by the diffusion of the solute-vacancy complex during aging treatment. The grain boundary segregation plays an important role in the nucleation and growth of VRC, GP Ⅱ zones, η＇ phase as well as η phase.

Grain boundary pre-precipitation and its contribution to enhancement of corrosion resistance of Al-Zn-Mg alloy

High temperature pre-precipitation （HTPP）took place in7005 alloy at various temperatures after solution treatment and itsinfluence on mechanical properties, corrosion behaviors and microstructure of the alloy was investigated using tensile test, intergranular corrosion （IGC） test, slow strain rate testing （SSRT）, together with microstructural examinations. It is found that Vickers hardness of the aged alloy decreases gradually with decreasing the HTPP temperature, and almost a reverse trend of electrical conductivity is found compared to the hardness changes. Depending on the changes, two HTPP temperaturesof 440 and 420℃ were chosen for comparative study. Results reveal that HTPP alloy tempers exhibit higher resistance to stress corrosion cracking （SCC） and IGC than none pre-precipitate one with an acceptable strength loss due to the substantial enhancement of distribution discontinuity of the coarse grain boundary precipitates （GBPs）, and the coarsening and interspacing effect on GBPs becomes more obvious with decreasing the pre-precipitation temperature.

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.

Molecular dynamics simulation of fracture behaviors of <110> tilt grain boundaries in γ-TiAl

Molecular dynamics(MD) simulations were carried out to study the fracture behaviors of several symmetric tilt grain boundaries in γ-Ti Al bicrystals with <110> misorientation axes. Tensile deformation along direction perpendicular to grain boundary was simulated under various strain rates and temperatures. The results indicate that the relative orientation of the grains and the presence of certain atom units are two critical factors of the interface structure affecting the stress required for dislocation nucleation. Dislocations nucleate and extend at or near the symmetric tilt grain boundaries during the tensile deformation of Σ3(111) 109.5°, Σ9(221) 141.1° and Σ27(552) 148.4° interfaces. For Σ27(115) 31.6° and Σ11(113) 50.5° interfaces, the interfaces fractured directly in a cleavage manner due to no dislocation emitted from the boundary. The tensile fracture mechanisms of the bicrystals are that micro-cracks nucleate at the grain boundary and propagate along the interface. The variance of crack propagation is whether there is accommodation of plastic region at the crack tips.