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.

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.

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.

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.

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.

Behaviors of Lanthanum and Cerium on Grain Boundaries in Carbon Manganese Clean Steel

The behaviors of La and Ce on gram boundaries in carbon manganese clean steel were investigated by high-reso- lution transmission elecetron microscope （HRTEM）, scanning elecetron microscopy（SEM ）, energy dispersive spectrometer （EDS） and X-ray diffraction（XRD） analysis. The existing forms of rare earths （RE） in clean steel were as follows： dissolved in sohd solution, forming inclusion or second phase containing RE （RE-Fe-P, La-P, Fe-La eutectic and Fe-Ce phase）. The dissolved La or Ce segregated at grain boundaries. The segregation of both S and P at gram boundaries was reduced with suitable RE content. The impact toughness of the steel was improved obviously. La and Ce had effecets on purifying molten steel and modifying inclusions in clean steel, whereas with excessive La or Ce, La-Fe-P, La-P and Fe-La eutecetic phase or Ce-Fe-P and Fe-Ce intermetallic compound would form along grain boundaries, causing the impact energy to decrease significantly.

Influence of sub-grain boundaries on quenching process of an Al-Zn-Mg-Cu alloy

The effects of sub-grain boundaries on the quenching sensitivity and the precipitation behavior in Al-7.01Zn-1.26Mg- 1.43Cu alloy were investigated by an end-quenching test. Specimens were solution treated at 440 ℃ and 480 ℃ to get different recrystallization fractions, respectively. The results show that the maximum hardness value of the Al-Zn-Mg-Cu alloy can be improved by the sub-grain boundaries, but the depth of age-hardening layer decreases significantly. The precipitation temperature and the activation energy are reduced by the changes of surface energy, which is induced by sub-grain boundaries. So, the precipitation process from η phase to η phase becomes much easier. In this way, an increase in the number of sub-grain boundaries promotes the precipitation of MgZn2 particles, especially η＇-MgZn2.

Effect of the frequency of high-angle grain boundaries on the corrosion performance of 5wt%Cr steel in a CO2 aqueous environment

The corrosion behavior of 5 wt%Cr steel tempered at different temperatures was investigated by immersion testing and electrochemical testing in a CO_2 aqueous environment. When the tempering temperature exceeded 500℃, the corrosion rate increased. The corrosion layers consisted of Cr-rich compounds, which affected the corrosion behaviors of the steels immersed in the corrosive solution. The results of electrochemical experiments demonstrated that 5 wt%Cr steels with different microstructures exhibited pre-passivation characteristics that decreased their corrosion rate. Analysis by electron back-scattered diffraction showed that the frequency of high-angle grain boundaries(HAGBs) and the corrosion rate were well-correlated in specimens tempered at different temperatures. The corrosion rate increased with increasing HAGB frequency.

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

The model of dislocations was used to construct the model of grain boundary (GB) with pure rare earths, and rare earth elements and impurities. The influence of the interaction between rare earth elements and impurities on the cohesive properties of 5.3° low angle GB of Fe was investigated by the recursion method. The calculated results of environment sensitive embeding energy( E ESE ) show that the preferential segregation of rare earth elements towards GBs exists. Calculations of bond order integrals (BOI) show that rare earth elements increase the cohesive strength of low angle GB, and impurities such as S, P weaken the intergranular cohesion of the GB. So rare earth element of proper quantity added in steel not only cleanses other harmful impurities off the GBs, but also enhances the intergranular cohesion. This elucidates the action mechanism of rare earth elements in steel from electronic level and offers theoretical evidence for applications of rare earth elements in steels.

CYCLIC HARDENING BEHAVIOR OF POLYCRYSTALS WITH PENETRABLE GRAIN BOUNDARIES:TWO-DIMENSIONAL DISCRETE DISLOCATION DYNAMICS SIMULATION

A two-dimensional discrete dislocation dynamics （DDD） technology by Giessen and Needleman （1995）, which has been extended by integrating a dislocation-grain boundary interaction model, is used to computationally analyze the micro-cyclic plastic response of polycrystals containing micron-sized grains, with special attentions to significant influence of dislocationpenetrable grain boundaries （GBs） on the micro-plastic cyclic responses of polycrystals and underlying dislocation mechanism. Toward this end, a typical polycrystalline rectangular specimen under simple tension-compression loading is considered. Results show that, with the increase of cycle accumulative strain, continual dislocation accumulation and enhanced dislocation-dislocation interactions induce the cyclic hardening behavior; however, when a dynamic balance among dislocation nucleation, penetration through GB and dislocation annihilation is approximately established, cyclic stress gradually tends to saturate. In addition, other factors, including the grain size, cyclic strain amplitude and its history, also have considerable influences on the cyclic hardening and saturation.

ANELASTIC RELAXATIONS ASSOCIATED WITH LOCAL DISORDERING AT GRAIN BOUNDARIES

Internal friction and micro-creep measurements were performed with high-purity aluminium bamboo-crystal specimens.The relaxation strength was found to decrease with the decrease of temperature and became zero at about 0.4 T_m(T_m is the melting temperature).This re- flects the occurrence of local disordering in the bamboo boundary region at this temperature. This result conforms to the picture of grain-boundary disordering constructed by atomic simulation studies.

Low-Angle Grain Boundaries in Sublimation Grown 6H-SiC Crystals

High-resolution X-ray diffractometry(HRXRD)was used to assess the quality of 6H-SiC crystals grown by sublimation method.The results show the occurrence of low-angle grain boundaries(LB)is close relative to the inclination of the crystal interface.At the central faceted region with 0°inclination the crystal is of high structural perfection.However,at the region close to the facet with less than 5°inclination LB occurs slightly and at the region close to the peripheral polytype ring with more than 5°inclination LB defect occurs heavily.The density of LB can be drastically reduced by decreasing radial temperature gradient that determines the shape of the crystal growth interface.

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.

Multiple time step molecular dynamics simulation for interaction between dislocations and grain boundaries

A multiple time step algorithm, called reversible reference system propagator algorithm, is introduced for the long time molecular dynamics simulation. In contrast to the conventional algorithms, the multiple time method has better convergence, stability and efficiency. The method is validated by simulating free relaxation and the hypervelocity impact of nano-clusters. The time efficiency of the multiple time step method enables us to investigate the long time interaction between lattice dislocations and low-angle grain boundaries.

Diffusion behavior of helium in titanium and the effect of grain boundaries revealed by molecular dynamics simulation

The microstructures of titanium（Ti）, an attractive tritium（T） storage material, will affect the evolution process of the retained helium（He）. Understanding the diffusion behavior of He at the atomic scale is crucial for the mechanism of material degradation. The novel diffusion behavior of He has been reported by molecular dynamics（MD） simulation for the bulk hcp-Ti system and the system with grain boundary（GB）. It is observed that the diffusion of He in the bulk hcp-Ti is significantly anisotropic（the diffusion coefficient of the [0001] direction is higher than that of the basal plane）,as represented by the different migration energies. Different from convention, the GB accelerates the diffusion of He in one direction but not in the other. It is observed that a twin boundary（TB） can serve as an effective trapped region for He.The TB accelerates diffusion of He in the direction perpendicular to the twinning direction（TD）, while it decelerates the diffusion in the TD. This finding is attributable to the change of diffusion path caused by the distortion of the local favorable site for He and the change of its number in the TB region.

Stress Field of Non-equilibrium Grain Boundaries in Nano-crystalline Metals

Introducing the stress distribution near grain boundaries to improve the dislocation pileup model for the Halt-Petch (H-P) relation, the continuous distribution of dislocations in the pileup could be solved by means of Tschebysheff polynomials for the Hilbert transformation. An analytical formula of the stress intensity factor for the dislocation pileup is obtained. The reverse H-P relation may be explained by the modified dislocation-pileup-model.

Bismuth nanosheets with rich grain boundaries for efficient electroreduction of CO_(2)to formate under high pressures

Electrochemical CO_(2)reduction reaction(CO_(2)RR)driven by sustainable energy has emerged as an attractive route to achieve the target of carbon neutral.Formate is one of the most economically viable products,and electrocatalytic CO_(2)RR to formate is a promising technology.High-pressure H-cell electrolyzer is easy to operate and allows high CO_(2)solubility for realizing high current density,but the design of highly efficient catalysts for working under high CO_(2)pressures remains challenging.Bismuth-based catalysts exhibit high formate selectivity,but suffer from limited activity.Here,we report a high-performance catalyst,which is derived from BiPO_(4)nanopolyhedrons during electrocatalytic CO_(2)RR to formate in neutral solution under high CO_(2)pressures.A high partial current density of formate(534 mA cm^(−2))and formate formation rate(9.9 mmol h^(−1) cm^(−2))with a formate Faradaic efficiency of 90%have been achieved over BiPO_(4)-derived catalyst at an applied potential of−0.81 V vs.RHE under 3.0 MPa CO_(2)pressure.We discover that BiPO_(4)nanopolyhedrons evolve into metallic Bi nanosheets with rich grain boundaries in electrocatalytic CO_(2)RR under high CO_(2)pressures,and the grain boundaries of the BiPO_(4)-derived catalyst play a vital role in promoting electrocatalytic CO_(2)RR to formate.Our theoretical studies reveal that the charge redistribution occurs at the grain boundaries of Bi surface,and this promotes CO_(2)activation and increases HCOO^(*)intermediate stability,thus making the pathway for CO_(2)RR to formate more selective and energy-favorable.This work not only demonstrates a highly efficient catalyst for CO_(2)RR to formate but also discovers a unique feature of catalyst evolution under high CO_(2)pressures.

Carrier Transport Across Grain Boundaries in Polycrystalline Silicon Thin Film Transistors

We established a model for investigating polycrystalline silicon（poly-Si） thin film transistors（TFTs）.The effect of grain boundaries（GBs） on the transfer characteristics of TFT was analyzed by considering the number and the width of grain boundaries in the channel region,and the dominant transport mechanism of carrier across grain boundaries was subsequently determined.It is shown that the thermionic emission（TE） is dominant in the subthreshold operating region of TFT regardless of the number and the width of grain boundary.To a poly-Si TFT model with a 1 nm-width grain boundary,in the linear region,thermionic emission is similar to that of tunneling（TU）,however,with increasing grain boundary width and number,tunneling becomes dominant.

Effects of grain boundaries on electrical property of copper wires

By means of annealing at different temperatures, the copper wires with various numbers of grain boundaries were achieved. And the resistivity of copper wires was measured. The results show that with increasing the number of grain boundaries, the resistivity of copper wires increases, the relationship between the number of grain boundaries and the resistivity of cooper wires can be expressed as y =1.86×10 -8 e -0.90/ x . Unlike dislocation and lattice vacant sites, the curve of the grain boundary vs the resistivity is not linear. Grain boundary controls the general trend of the curve, but the type and the quantity of impurity controls the details of the curve.