Effect of grain boundary character on sink efficiency

The dependence of the width of void-denuded zones (VDZs) on grain boundary (GB) characters was investigated in Cu irradiated with He ions at elevated temperature. Dislocation loops and voids formed near GBs during irradiation were characterized by transmission electron microscopy, and GB misorientations and normal planes were determined by electron back-scatter diffraction. The VDZ widths at Σ3〈1 1 0〉 tilt GBs ranged from 0 to 24 nm and increased with the GB plane inclination angle. For non-Σ3 GBs, VDZ widths ranged from 40 to 70 nm and generally increased with misorientation angle. Nevertheless, there is considerable scatter about this general trend, indicating that the remaining crystallographic parameters also play a role in determining the sink efficiencies of these GBs. In addition, the VDZ widths at two sides of a GB show different values for certain asymmetrical GBs. Voids were also observed within GB planes and their density and radius also appeared to depend on GB character. We conclude that GB sink efficiencies depend on the overall GB character, including both misorientation and GB plane orientation.     

Bismuth nanoprecipitation at grain boundaries during microstructural evolution in (Sr, Ba)TiO3 ceramics

Metallic Bi nanoprecipitates (NPs) were observed at grain boundaries (GBs) in a series of Bi-doped Sr_1−xBa_xTiO₃ ceramics sintered at low temperature, using analytical electron microscopy. Most GBs fell into two groups, according to their local structure and chemistry, one with the NPs and the other with titania-based amorphous film. The solution of Ba into the lattice was only about one-third of the nominal value, and the remaining Ba dopants were driven into triple pockets or wetted the GBs during the sintering. Lower Ba doping initiated less liquid, resulting in a core–shell structure. Bi dopants were co-soluted with Ba, thereby suppressing the Bi segregation at GBs. The extra Bi could not diffuse out through the dewetted GB as fast as via the titania-based film, compelling them to precipitate locally. These metallic NPs may initiate several modes of polarization that increase the dielectric constants detected at 1 kHz.     

Solute Segregation to Grain Boundaries in Al: A First-Principles Evaluation

Solute-induced grain boundary(GB) strengthening is eff ective in improving the toughness and tensile strength of polycrystalline alloys. In this work, GB segregation behaviors of solute elements in Al alloys and their potential eff ects on GB binding have been systematically investigated from fi rst-principles energetics. The low-energy Σ3(111) and Σ11(113) are immune to vacancy segregation, while high-energy Al GBs, such as Σ13(320), Σ9(221), Σ5(210), and Σ5(310), can attract both vacancies and...     

金属材料疲劳损伤的界面效应

总结了不同金属材料在低周疲劳过程中典型的晶界、孪晶界、相界和微电子互连界面的损伤开裂行为. 纯Cu中疲劳裂纹萌生的难易顺序为: 小角度晶界、驻留滑移带和大角度晶界. 对于纯Cu与铜合金中退火孪晶界, 是否萌生疲劳裂纹与合金成分有关, 随合金元素的加入降低了层错能, 退火孪晶界相对容易萌生疲劳裂纹. 对于Cu--Ag二元合金, 由于存在不同的晶界和相界面, 是否萌生疲劳裂纹取决于界面两侧晶体的取向差, 通常两侧取向差大的界面容易萌生疲劳裂纹. 在微电子互连界面中, 疲劳裂纹萌生位置与焊料成分和时效时间有关,对于Sn--Ag/Cu互连界面, 疲劳裂纹通常沿焊料与界面化合物结合处萌生; 对于Sn--Bi/Cu互连界面, 随时效时间增加会出现明显的由于Bi元素偏聚造成的界面脆性.     

Atomistic simulations of grain boundary segregation in nanocrystalline yttria-stabilized zirconia and gadolinia-doped ceria solid oxide electrolytes

Hybrid Monte Carlo–molecular dynamics simulations are carried out to study defect distributions near Σ5(3 1 0)/[0 0 1] pure tilt grain boundaries (GBs) in nanocrystalline yttria-stabilized zirconia and gadolinia-doped ceria. The simulations predict equilibrium distributions of dopant cations and oxygen vacancies in the vicinity of the GBs where both materials display considerable amounts of dopant segregation. The predictions are in qualitative agreement with various experimental observations. Further analyses show that the degree of dopant segregation increases with the doping level and applied pressure in both materials. The equilibrium segregation profiles are also strongly influenced by the microscopic structure of the GBs. The high concentration of oxygen vacancies at the GB interface due to lower vacancy formation energies triggers the dopant segregation, and the final segregation profiles are largely determined by the dopant–vacancy interaction.     

Effect of crystallographic orientation and grain boundary character on fatigue cracking behaviors of coaxial copper bicrystals

Four coaxial copper bicrystals were employed to study the slip morphologies and fatigue cracking behaviors during cyclic deformation. Three of them had high-angle grain boundaries (GBs) with nearly the same misorientation and one bicrystal had a twin boundary (TB). Different slip bands (SBs) operated near the GBs and TB, generating different dislocation arrangements, which are mainly determined by the crystallographic orientations of the component grains. The GBs suffered impingement or shear damage caused by slip difference from both sides. It is suggested that there is an energy increase in the interfaces between matrix and persistent slip bands (PSBs), GBs and TBs per cycle during cyclic deformation due to the accumulation of lattice defects, which would make the interface unstable. After a certain number of cycles, fatigue cracks initiated firstly at GBs for some bicrystals while fatigue cracking occurred preferentially at PSBs for the others. It is confirmed that the energy growth rate is an increasing function of the shear stress, strain amplitude and strain incompatibility, which results from slip differences on both sides of the interfaces. Interfaces with different energies and strain incompatibilities have different fatigue cracking resistance. It is found that GBs with defective and complex structure, and hence high interfacial energy accompanied by high modulus of the residual GB dislocation (GBD), are preferential sites for fatigue cracking, while the fatigue cracking appeared predominantly at PSBs when the modulus of the residual GBD is lower than that of a perfect dislocation with simple GB structure and low interfacial energy. The present model for the energy can predict well which kind of interface would form cracks preferentially during cyclic deformation in one coaxial bicrystal and which GB would need more cycles to initiate fatigue cracking between coaxial bicrystals with different GB characters.     

Grain boundary and interface chemistry of an Nd-Fe-B-based sintered magnet

The compositions of grain boundaries (GBs) and other interfaces surrounding Nd₂Fe₁₄B grains in commercial Nd-Fe-B sintered magnets have been investigated by laser-assisted three-dimensional atom probe to understand the mechanism of the coercivity enhancement by post-sinter annealing. While only a slight segregation of Nd and Pr to the GBs was confirmed in the as-sintered sample, a thin Nd-rich amorphous phase layer was observed along the GBs with Cu segregation to the interfaces in the annealed sample. The segregation of Cu to NdO_x/Nd₂Fe₁₄B interfaces was also found, suggesting that the Nd₂Fe₁₄B grains are enveloped by a Cu-enriched layer after the annealing. The concentration of Fe + Co in the thin GB layer was found to be as high as 65 at.%, and a model amorphous film processed by sputtering with the same composition as the thin GB layer was found to be ferromagnetic. Ferromagnetic behavior of the thin GB layer suggested that Nd₂Fe₁₄B grains are magnetically coupled. The coercivity mechanism of the sintered magnets is discussed based on these new findings.     

Grain Boundary Segregation of Interstitial and Substitutional Impurity Atoms in Alpha-Iron

The macroscopic behavior of polycrystalline materials is influenced by the local variation of properties caused by the presence of impurities and defects. The effect of these impurities at the atomic scale can either embrittle or strengthen grain boundaries (GBs) within. Thus, it is imperative to understand the energetics associated with segregation to design materials with desirable properties. In this study, molecular statics simulations were employed to analyze the energetics associated with the segregation of various elements (helium, hydrogen, carbon, phosphorous, and vanadium) to four 〈100〉 (Σ5 and Σ13 GBs) and six 〈110〉 (Σ3, Σ9, and Σ11 GBs) symmetric tilt grain boundaries in α-Fe. This knowledge is important for designing stable interfaces in harsh environments. Simulation results show that the local atomic arrangements within the GB region and the resulting structural units have a significant influence on the magnitude of binding energies of the impurity (interstitial and substitutional) atoms. These data also suggest that the site-to-site variation of energies within a boundary is substantial. Comparing the binding energies of all 10 boundaries shows that the Σ3(112) boundary possesses a much smaller binding energy for all interstitial and substitutional impurity atoms among the boundaries examined in this study. Additionally, based on the Rice–Wang model, our total energy calculations show that V has a significant beneficial effect on the Fe grain boundary cohesion, while P has a detrimental effect on grain boundary cohesion, much weaker than H and He. This is significant for applications where extreme environmental damage generates lattice defects and grain boundaries act as sinks for both interstitial and substitutional impurity atoms. This methodology provides us with a tool to effectively identify the local as well as the global segregation behavior that can influence the GB cohesion.     

Evolution of initial grain boundaries and shear bands in Cu bicrystals during one-pass equal-channel angular pressing

The evolution of grain boundaries (GBs) and shear bands in Cu bicrystals during one-pass equal-channel angular pressing (ECAP) was systematically investigated by various techniques. Four Cu bicrystals were designed to make GBs with angles of 0°, 45°, 90° and 135° with respect to the intersection plane (IP) of the ECAP die. After ECAP, the shear bands and the GB orientations in the four bicrystals displayed distinct behaviors due to the difference in the initial GB directions and the special crystallographic orientation of the component grains. Based on the experimental results, it is suggested that the initial GBs have a remarkable influence on the shear deformation behaviors of the adjacent regions, and the deformation regions far from the GBs are mainly controlled by the crystallographic orientations. The present investigations further demonstrate that shear deformation along the normal of the IP plays an important role in the deformation of Cu bicrystals.     

In situ TEM observation of grain annihilation in tricrystalline aluminum films

Capillarity-driven grain boundary (GB) motion in Al tricrystalline thin films has been investigated by in situ transmission electron microscopy at intermediate temperatures. The GBs were observed to move erratically, with alternating periods of motion and stagnation, followed by rapid shrinkage of the grain and eventual annihilation accompanied by the emission of dislocations. The absence of measured deformation and grain rotation during the GB motion suggests that it is not associated with shear-migration coupling. This is in contrast to observations on the stress-driven motion of planar GBs. The present results can be interpreted by the absence of deformation associated with low internal applied stress or alternatively by a low shear-migration coupling factor. In both cases, a large amount of atomic shuffling is needed to account for the migration of grain boundaries.     

Mechanical behavior of Σ tilt grain boundaries in nanoscale Cu and Al: A quasicontinuum study

Molecular simulations using the quasicontinuum method are performed to understand the mechanical response at the nanoscale of grain boundaries (GBs) under simple shear. The energetics and mechanical strength of 18 Σ 〈1 1 0〉 symmetric tilt GBs and two Σ 〈1 1 0〉 asymmetric tilt GBs are investigated in Cu and Al. Special emphasis is placed on the evolution of far-field shear stresses under applied strain and related deformation mechanisms at zero temperature. The deformation of the boundaries is found to operate by three modes depending on the GB equilibrium configuration: GB sliding by uncorrelated atomic shuffling, nucleation of partial dislocations from the interface to the grains, and GB migration. This investigation shows that (1) the GB energy alone cannot be used as a relevant parameter to predict the sliding of nanoscale high-angle boundaries when no thermally activated mechanisms are involved; (2) the E structural unit present in the period of Σ tilt GBs is found to be responsible for the onset of sliding by atomic shuffling; (3) GB sliding strength in the athermal limit shows slight variations between the different interface configurations, but has no apparent correlation with the GB structure; (4) the metal potential plays a determinant role in the relaxation of stress after sliding, but does not influence the GB sliding strength; here it is suggested that the metal potential has a stronger impact on crystal slip than on the intrinsic interface behavior. These findings provide additional insights on the role of GB structure in the deformation processes of nanocrystalline metals.     

Tracer diffusion of Au and Cu in a series of near Σ=5 (310)[001] symmetrical Cu tilt grain boundaries

Grain boundary diffusion of Au and Cu was measured in a series of Cu bicrystals with symmetrical near Σ=5, Θ=36.9° (310)[001] CSL tilt grain boundaries (GBs) using the radiotracer and the serial sectioning technique. The orientations of the bicrystals were very precisely determined with the Kossel technique where all three macroscopic parameters describing the orientations of the grains in the bicrystal were evaluated. The tilt angles ranged from 33.21° to 39.26°. The GB diffusion of the radiotracers ¹⁹⁵Au and ⁶⁴Cu was measured as a function of tilt angle and temperature. In the investigated temperature range 1030–661 K the orientation dependence of both radiotracers shows a characteristic cusp not exactly at but slightly below the ideal Σ=5 CSL GB. The Arrhenius parameters, activation enthalpy and frequency factor, determined from lower temperature data adopt a maximum, again slightly before the ideal Σ=5 CSL GB. These features are discussed with respect to the accidental small twist and second tilt orientations and the corresponding dislocation network inherent in the investigated real GBs. With increasing temperature a negative deviation from a straight Arrhenius behaviour is observed. This result indicates a certain change in the GB structure in the temperature range above 800 K.     

Relation between precipitate-free zone width and grain boundary type in 7075-T7 Al alloy

The effect of grain boundary (GB) type on precipitate-free zone (PFZ) width in friction stir-processed 7075-T7 Al alloy is investigated by transmission electron microscopy (TEM) and stereology. The average half width of PFZs at random GBs is 70.4 ± 0.7 nm. For low-angle GBs, an apparent transition of PFZ half width is observed at a misorientation of 11°. For coincidence site lattice (Σ) GBs, only Σ1, Σ3 and Σ5 have smaller PFZ width than that of random GBs. Crystal-frame stereology is used to recover the GB plane distribution. It is found that the GB plane distribution is relatively isotropic for most Σ GBs. Low/high index plane combinations are observed for most Σ GBs; furthermore, most Σ GBs have both tilt and twist components. The combined results of TEM and stereology suggest that smaller PFZ width is associated only with low Σ GBs since the formation and growth of PFZs at GBs depends closely on the core structure, in addition to the geometric structure of GBs.     

A new investigation of copper's role in enhancing Al–Cu interconnect electromigration resistance from an atomistic view

An explanation of why Cu prolongs the electromigration lifetime of Al–Cu interconnects in comparison to Al is provided based on atomistic calculations. Copper preferentially segregates to the grain-boundary (GB) interstitial sites. The overall GB diffusivity is reduced with Cu segregation at GB sites. Calculation results predict that in Al(Cu) lines, Cu will diffuse first, with Al diffusion essentially suppressed because of a higher diffusion activation energy. The activation energy for Cu incubation diffusion is calculated to be 0.95 eV. The predictions are in excellent agreement with experiments.     

Quasicontinuum study of incipient plasticity under nanoscale contact in nanocrystalline aluminum

Atomistic simulations using the quasicontinuum method are performed to examine the mechanical behavior and underlying mechanisms of surface plasticity in nanocrystalline aluminum with a grain diameter of 7 nm deformed under wedge-like cylindrical contact. Two embedded-atom method potentials for Al, which mostly differ in their prediction of the generalized stacking and planar fault energies, and grain boundary (GB) energies, are used and characterized. The simulations are conducted on a randomly oriented microstructure with 〈1 1 0〉-tilt GBs. The contact pressure–displacement curves are found to display significant flow serration. We show that this effect is associated with highly localized shear deformation resulting from one of three possible mechanisms: (1) the emission of partial dislocations and twins emanating from the contact interface and GBs, along with their propagation and intersection through intragranular slip, (2) GB sliding and grain rotation and (3) stress-driven GB migration coupled to shear deformation. Marked differences in mechanical behavior are observed, however, as a function of the interatomic potential. We find that the propensity to localize the plastic deformation at GBs via interface sliding and coupled GB migration is greater in the Al material presenting the lowest predicted stacking fault energy and GB energy. This finding is qualitatively interpreted on the basis of impurity effects on plastic flow and GB-mediated deformation processes in Al.     

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 °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 D_c=7.8×10^?5exp[–1.46/(kT)]; the apparent diffusion coefficient of Bi atoms D_i^A=7.66×10^at+bexp[–1.76/(kT)], where a=8.45×10^?8 and b=–13.37.     

Wetting of molybdenum grain boundaries by nickel: effect of the boundary structure and energy

The structural effect of the penetration of nickel along symmetrical [101] tilt grain boundaries (GBs) in two different molybdenum bicrystals is investigated. The selection of GBs (Σ=3{121} and Σ=11{323}) is governed by their different energy so that a different penetration behaviour is expected. The temperature of treatment is 1350°C, i.e. above the eutectic temperature. The analysis of the Mo–Ni phase formed on the surface of the bicrystal, the concentration profile along the GB and the identification of the nanophases present at the GB is performed by using several experimental techniques from microscopic to nanoscopic scales. Important differences in the penetration of nickel are found for the two investigated GBs.     

Grain-boundary diffusion in B2 intermetallic compounds: effect of ordering on diffusion in the Fe3Al and FeCo compounds

Grain-boundary (GB) self-diffusion in the Fe₃Al and FeCo compounds was investigated in the B-kinetic regime by the radiotracer method over temperature ranges including the bulk order-disorder transition temperatures. For iron diffusion in Fe₃Al the A2–B2 transition did not lead to any modification of the Arrhenius behavior, while a slight decrease of the triple product values below the B2-DO₃ transition is observed. In FeCo both for iron and cobalt the A2–B2 transition evokes a decrease in the pre-exponential factor of the triple product, while the diffusion activation energy is not altered. These results are tentatively interpreted in view of recent segregation experiments carried out on the free surfaces of the compounds and it is proposed that owing to segregation the order–disorder transition temperature can be considerably different in GBs from that in the bulk.     

Carbon segregation and inclusions effects on surface fracture morphology of a 12% chromium stainless steel

Martensitic 12% chromium stainless steel is generally used for the manufacture of water vapour turbine blades. This material, under these environmental conditions, develops fatigue corrosion with failure as a result of the segregation of certain constituent elements such as phosphorus (P) and sulphur (S),^[1–3] or the presence of some types of inclusions.^[2–4] To be able to understand and explain these phenomena, in situ characterization of the fractured surfaces were performed for two types of samples: steel 1 as manufactured turbine material whose fracture mode is intergranular and steel 2 issued from last stage turbine blades after 100 000 h service at 40 °C whose fracture mode is transgranular. The techniques used for characterization were scanning electron microscopy (SEM) coupled with the x-ray analysis by energy dispersive spectroscopy (EDS), and auger electron spectroscopy (AES). The Auger results enabled the understanding of the brittle to ductile transition for the material by showing the simultaneous diffusion of carbon from grain boundaries (GB) to grains (G) and chromium from G to GB. Furthermore, the heavy segregation of phosphorus at the GBs could explain the intergranular crack rupture traces observed in steel 2. SEM observations coupled with EDS analysis showed the presence of different types of non-metallic inclusions such as silicon-based complex inclusions and manganese sulfides (MnS). The presence of silicon-based complex inclusions at GB could explain the intergranular fracture mode previously reported. The characterization of the fracture appearance suggests also that MnS inclusions can act as nucleation sites for secondary microcracks at the GB level that were observed after service.     

Electrical resistivity of fully-relaxed grain boundaries in nanocrystalline Cu

Electrical resistivity of grain boundaries (GBs) was determined in nanocrystalline (nc) Cu specimens prepared by magneto-sputtering and subsequent annealing. Extrapolating the microstrain dependence of GB resistivity, we derived electrical resistivity of GBs in a fully-relaxed state in Cu, being 2.04 × 10⁻¹⁶ Ω m².