Random Grain Boundaries Research Articles

Enhancing mechanical property and corrosion resistance of Al0.3CoCrFeNi1.5 high entropy alloy via grain boundary engineering

In the present study, to improve the performances of Al0.3CoCrFeNi1.5 high entropy alloys (HEAs), grain boundary character distribution (GBCD) of Al0.3CoCrFeNi1.5 HEA has been optimized by an appropriate thermo-mechanical processing. The experiment results showed that the fraction of low-Σ coincidence site lattice (CSL) boundaries could reach approximately 80 % through cold rolling with deformation of 8 % and subsequent annealing at 1050 °C for 5 min. The reason for GBCD optimization could be attributed to sufficient strain-induced boundary migration (SIBM) or grain growth after recrystallization. While recrystallization is not favorable for optimizing GBCD. The mechanical properties and corrosion resistance have been enhanced, with a more pronounced improvement observed in the corrosion resistance. The corrosion current density icorr of the GBEM specimen stands at 0.23 μA∙cm−2, representing a reduction of 66 % in comparison to the BM specimen (0.68 μA∙cm−2). The improvement of corrosion resistance of Al0.3CoCrFeNi1.5 HEA resulted from the discontinuous random grain boundaries (RGBs) broken by the high fraction of low-ΣCSL boundaries, especially Σ3 boundaries suppressed the propagation of corrosion crack.

Statistical analysis of vertically stacked nanosheet complementary FET based on polycrystalline silicon with multiple grain boundaries

In this study, a complementary field-effect transistor (CFET) based on a polycrystalline silicon (poly-Si) stacked-nanosheet (NS) structure with a grain boundary (GB) is designed and analyzed using a technology computer-aided design (TCAD) simulation. The advantage of the CFET using a poly-Si is that the active cell region can be reduced by 50 % because the p-type transistors are vertically stacked on the n-type transistors. In addition, it is possible to replace the conventional CMOS process and fabricate a three-dimensional vertically stacked structure at a low cost. To consider the effect of the GB in poly-Si, we assumed that there is a single GB at the center of the body region. By optimizing the geometrical parameters of the proposed CFET, the transfer characteristics of the NMOS and PMOS transistors, such as the threshold voltage (Vth), on current (Ion), off current (Ioff), and subthreshold swing (SS), are symmetrical. The proposed CFET demonstrated a superior logic performance of NML = 0.299 V and NMH = 0.297 V at an operation voltage of VDD = 0.65 V. To consider random GBs in the poly-Si, we assumed that five GBs existed in the proposed CFET, and the variation in CMOS logic inverter characteristics are statistically analyzed. As a result, the RSDs for Vm of the NMOS and PMOS transistors are 2.067 % and 0.293 %, and the RSDs of the pull-down delay time (tpHL) and pull-up delay time (tpLH) are 5.320 % and 3.244 %, respectively. An acceptor-like traps with high trap density are dominant in the proposed CFET, and this trend is similar across the 1024 samples. Nevertheless, most of the differences are within 5 % and the proposed CFET exhibited stability against GBs and the potential to replace the conventional CMOS logic inverters.

Experimental study on the hydrogen diffusion across an individual grain boundary in pure nickel by scanning Kelvin probe force microscopy

There are few existing experimental studies on the controversial diffusion behavior of hydrogen atoms across an individual grain boundary (GB). In this study, by combining Electron Back Scattered Diffraction (EBSD) and scanning Kelvin probe force microscopy (SKPFM) techniques, the transverse diffusion behavior of hydrogen atoms across a random GB with a misorientation of 45° within the directionally solidified high purity nickel was directly observed. The results suggest that the hydrogen atoms diffused perpendicular to the studied GB will be trapped by this GB, resulting in hydrogen segregation at the GB. In addition, the studied GB acts as a two-dimensional barrier that can block the transverse diffusion of hydrogen atoms. This present study reveals the real role played by a specific random GB on the hydrogen transverse diffusion and enriches the existing experimental research for intergranular diffusion.

Hydrogen Video Imaging System for Visualizing Microstructure-Dependent Hydrogen Diffusion Behaviors in Polycrystalline Metals

Hydrogen diffusion in polycrystalline metals is known to depend on microstructure. The hydrogen-microstructure interactions have been extensively studied last decades, but the microstructure-dependent hydrogen diffusion behavior is still unclear. To clarify the hydrogen diffusion behavior, it is necessary to visualize the time variations of the microscopic hydrogen distribution in polycrystalline metals. Thus, we developed a hydrogen video imaging system (HVIS) in this study to analyze the hydrogen distribution in polycrystalline metals with sub-micrometer spatial and video-rate time resolutions. The inexpensive and atmospheric-control-free system is expected to be widely used as a versatile approach for analyzing the hydrogen-microstructure interaction in detail.Pure polycrystalline Ni (thickness: 125 µm) was used as a specimen. The specimen was electrochemically polished at a constant voltage of 50 V in a mixed solution of perchloric acid and acetic acid. The thickness was approximately 110 µm after polishing. Subsequently, a polyaniline layer (PANI) was polymerized on one side of pure Ni. The specimen was set to the acrylic cell, which is used to preserve a 0.1 M NaOH aqueous solution. So, only the bare Ni side of the specimen was exposed to the 0.1 M NaOH solution. Electrochemical hydrogen charging was conducted at the bare Ni side of the specimen at a constant current density of -10 A / m2. An inverted optical microscope was used to observe the color distribution of the PANI side. In our previous studies,1-3) it has been clarified that PANI changes its color due to the reaction with hydrogen in metals. Thus, the distribution of hydrogen permeated through pure polycrystalline Ni can be observed as a color distribution of PANI during hydrogen charging.The color of PANI was purple before the hydrogen charging. After 20 h of hydrogen charging, the color of PANI partially turned white. If PANI reacts with hydrogen, the color changes from purple or dark blue to yellow or transparent.1,2) Therefore, the local whitening of PANI is thought to be caused by the reaction with atomic state hydrogen permeated through pure polycrystalline Ni. The number of color changed areas increased with time during hydrogen charging. After 120 h of hydrogen charging, the specimen was immersed in a 1 M NaOH aqueous solution to remove PANI. Subsequently, the microstructure of pure polycrystalline Ni was analyzed using FE-SEM and EBSD. It was found that the color changed area of PANI corresponded to the grain boundaries (GBs) of pure Ni. This suggests that the GBs in pure Ni are preferential hydrogen diffusion paths. Furthermore, the clear color change of PANI was observed at the random GBs, while the whitening scarcely occurred at the Σ3 GBs, indicating that the preferential hydrogen diffusion mainly occurred at the random GBs. The results showed that HVIS can clarify the microstructure-dependent hydrogen diffusion in polycrystalline metals.

Effect of grain boundary engineering on corrosion behavior of 316 L stainless steel bipolar plate in proton exchange membrane fuel cells environment

This study illustrates the effect of grain boundary engineering (GBE) on the corrosion behavior of 316 L stainless steel (SS) in a proton exchange membrane fuel cells (PEMFCs) environment. It shows that the GBE increased the density of grain boundary and the coincidence site lattice (CSL) performes a better corrosion resistance, a preferential corrosion phase that the impurity elements are more likely biased at during the cast, the Random grain boundaries(RGBs) decreases. Furthermore, the texture on GBE2's closed-packed (111) plane reduces the surface atoms' dissolution velocity, thereby, decreasing the thermodynamic tendency to form dense corrosion films and nucleation kinetics. The above combined reasons lead to the lowest corrosion resistance of GBE2.

Enhancement of the resistance to hydrogen embrittlement by tailoring grain boundary characteristics in a low carbon high strength steel

In this work, the feasibility of using “grain boundary engineering” to reduce the susceptibility to hydrogen embrittlement in a low carbon low alloy steel was examined. By adding Cu element, the fraction of random grain boundary (RGB) exhibited the highest value in the steel with 1%Cu, while the fraction of special grain boundary (SGB) showed a monotonical decline. The slow strain rate tensile (SSRT) test revealed that the elongation loss presented an increase with Cu addition increasing from 1 % to 3 %. This can be explained in terms of hydrogen diffusion, hydrogen trap and crack propagation. The steel with 1%Cu had a higher fraction of high angle grain boundary (HAGB), which contributed to a higher density of hydrogen traps and a lower hydrogen diffusion rate. Moreover, the steel with 1%Cu had the highest fraction of SGB (∑3, ∑5, ∑7 and ∑≥9), which was beneficial to the resistance to crack propagation. Under the combined effect of RGB and SGB, a higher resistance to hydrogen embrittlement was achieved in the steel with 1%Cu.

Simulation of Capacitorless DRAM Based on the Polycrystalline Silicon Nanotube Structure with Multiple Grain Boundaries.

In this study, a capacitorless one-transistor dynamic random-access memory (1T-DRAM), based on polycrystalline silicon (poly-Si) nanotube structure with a grain boundary (GB), is designed and analyzed using technology computer-aided design (TCAD) simulation. In the proposed 1T-DRAM, the 1T-DRAM cell exhibited a sensing margin of 422 μA/μm and a retention time of 213 ms at T = 358 K with a single GB. To investigate the effect of random GBs, it was assumed that the number of GB is seven, and the memory characteristics depending on the location and number of GBs were analyzed. The memory performance rapidly degraded due to Shockley-Read-Hall recombination depending on the location and number of GBs. In the worst case, when the number of GB is 7, the mean of the sensing margin was 194 µA/µm, and the mean of the retention time was 50.4 ms. Compared to a single GB, the mean of the sensing margin and the retention time decreased by 59.7% and 77.4%, respectively.

Unrevealing grain boundary mobility in the precipitate hardening high entropy alloys

Exploring the interactions between precipitates and grain boundaries (GBs) is of great important to tailor the high-temperature stability and mechanical property of precipitate hardened alloys. However, the influence of precipitate on GB stability in high entropy alloys (HEAs) is still uncovered at nanoscale. In this work, we investigate the effects of precipitate size and temperature on grain boundary migration (GBM) using molecular dynamic simulations. The results show that the GB stability is improved with the increase of the precipitate size, especially at low temperatures. Compared with the traditional dilute alloys, the strong atomic lattice distortion exits in HEAs, resulting in the localized high tensile/compressive stresses. Thus, GB bends towards the indeterminate direction due to the lattice distortion, different with the case bending towards precipitate in the dilute alloys. In addition, the lattice distortion makes dislocation nucleate at random GB region in HEA, which is different from that in dilute alloys. High temperature reduces lattice distortion and relieves the localized high stresses, thereby inhibits the nucleation rate of dislocations from GB. These results provide the fundamental messages for designing novel HEAs with excellent thermal stability.

Mathematical Description for the Hierarchy of Grain-boundary Structures

Polycrystalline materials are ubiquitous, and their macroscopic properties strongly depend on the defects in crystalline structures. Grain boundaries (GBs) are the interfaces between crystal grains, which admit unique atomic arrangements different from those of crystals. It is essential to reveal the polyhedral arrangement in GB atomic structures to identify the origin of structure-property relationships in polycrystalline materials. We found that the GB region can only be packed by the bulk or GB-type polyhedral units with minor variations. Moreover, the GB hierarchy directly follows the distribution of rational numbers that is represented by the Farey diagram. The singular GB is defined to be a GB packed by at the most two types of polyhedral units in a period, and any GB can be packed by the polyhedral units that form the singular GBs. This approach allows us to predict the polyhedral arrangement in any tilt GBs including random GBs.

Capturing the softening in T91 steel annealed with molten LBE through interfacial gradient plasticity

In order to study the effect of annealing with molten lead–bismuth eutectic alloy (mLBE) on the mechanical properties of T91 steel, micropillar compression tests were analyzed through the consideration of mechanical interface energy terms within gradient plasticity. The stress–strain curves of the micropillars showed significant stochastic effects, characterized by a different elastic and plastic behavior response for each pillar. Among the various pillars, some exhibited a similar trilinear behavior. Scanning electron microscopy (SEM) images of these specimens demonstrated localized slip deformation and slip planes after compression, while transmission electron microscopy (TEM) images showed the presence of a severe slip zone along the random grain boundaries (RGBs), indicating that the GBs played a dominant role in the deformation/slip. By employing interfacial gradient plasticity that can explicitly account for the presence of GBs, the trilinear response was captured, allowing for the determination of the mechanical interface parameter. As anticipated the pillars which underwent severe slip at the GBs had a lower value for the mechanical interface parameter. Annealing with mLBE can, therefore, in some cases result in softening in the overall stress–strain, as it lowers the mechanical interface energy of GBs.

Hydrogen-assisted intergranular fatigue crack initiation in metals: Role of grain boundaries and triple junctions

In this work, small-scale, low-cycle fatigue experiments on hydrogen charged nickel specimens are performed that highlight particular grain boundaries (GBs) and triple junctions as potential intergranular crack initiation sites. To understand the micromechanics and underlying physics, a dislocation density-based crystal plasticity model coupled with slip-rate based hydrogen transport model is developed. A fatigue indicator parameter (FIP) is also developed that models the crack initiation process by considering the contributions of accumulated plastic slip, GB normal stress, and local hydrogen concentration. Depending on the diffusivity, hydrogen binding energy, and misorientation, GBs are categorized as ‘special’ or ‘random’, and their role on hydrogen distribution is analysed using a model microstructure. Special GBs are ones with low diffusivity and high hydrogen binding energy whereas the random GBs have high diffusivity but low hydrogen binding energy. Complying with the experimental observations, the evolution of FIP with load cycles suggests certain triple junction configurations in the microstructure involving in the crack initiation process. For the case of uniform initial hydrogen concentration, special GBs are found to retain more hydrogen with load cycles primarily due to their low hydrogen diffusivity whereas the random GBs diffuse hydrogen out quickly to the bulk. The high hydrogen concentration and favourable stress state in the form of high hydrostatic stress spots generally found at triple junction of special/random GBs fulfil the necessary condition leading to an intergranular crack initiation.

Effects of grain boundary character distribution on hydrogen-induced cracks initiation and propagation at different strain rates in a nickel-saving and high-nitrogen austenitic stainless steel

The effect of grain boundary character distribution (GBCD) on hydrogen-induced cracks (HICs) initiation and propagation in nickel-saving austenitic stainless steel was investigated at different strain rates with electrochemical hydrogen charging. The fracture strength and elongation of specimens decreased as the strain rates decreased due to more hydrogen atoms being transported by mobile dislocations. HICs are more likely to initiate at random grain boundaries (RGBs) because of poor deformation coordination of adjacent grains at RGBs after hydrogen charging. Special boundaries (SBs) deflected HICs and hindered the propagation of HICs owing to a more stable boundary structure and less strain localization during slow strain rate tensile (SSRT) deformation with hydrogen charging. Furthermore, highly efficient distributions of SBs contribute to great resistance to hydrogen embrittlement.

An approach to regulating grain boundary network by introducing high fraction of ∑3n and serrated grain boundaries simultaneously in Fe-Ni based alloy

• A method for further optimization of GB character distribution in Fe-Ni based alloy is proposed. • Both high fraction of ∑3 n boundaries and SGBs can be introduced in Fe-Ni based alloy simultaneously. • The fraction of special triple junctions is further increased. • The formation of SGBs is associated with the preferential growth of γ′ precipitates towards the RGBs. Random grain boundaries (RGBs) as weak links has closely related to the initiation and propagation of cracks in intergranular corrosion, stress corrosion and hydrogen embrittlement, etc. Hence, Grain boundary engineering (GBE) is proposed which manipulates GB structure by introducing ∑3 n boundaries and disruption RGBs network to optimize materials properties. However, GBE is insufficient to optimize the whole grain boundary structure as theoretical maximum fraction of ∑3 n boundaries. In this paper, an approach is proposed which optimize the microstructure in Fe-Ni based alloy by increasing ∑3 n boundaries also simultaneously changing some of the rest RGBs into serrated grain boundaries (SGBs). Moreover, the formation mechanism of SGB in Fe-Ni based alloy is also clarified.

Statistical study on the effects of heterogeneous deformation and grain boundary character on hydrogen-induced crack initiation and propagation in twining-induced plasticity steels

The initiation and propagation of hydrogen-induced cracks (HICs) in twining-induced plasticity (TWIP) steel were quantificationally explored based on the HIC statistics at a macro level and a micro level by slow strain rate tensile (SSRT) with in-situ hydrogen-charging and electron microanalysis. The heterogeneous deformation and grain boundary character determines a HIC initiation. The slip transfer parameter m′ < 0.93 and the minimum residual Burgers vector of residual dislocations on a grain boundary br > 0.19 were the critical condition for HIC initiation. Moreover, HICs prone to initiate and propagate along random grain boundaries (RGBs), while the Σ3 grain boundaries and vice.

A crystal plasticity model with an atomistically informed description of grain boundary sliding for improved predictions of deformation fields

Crystal plasticity (CP) is a powerful meso-scale technique for deformation modeling in polycrystalline materials. Crystal plasticity models typically do not include an explicit description of grain boundary (GB) sliding, which could lead to inaccurate predictions of strain distributions, especially in the vicinity of GBs. In the present study, a CP model is developed that includes GB sliding as an additional deformation mechanism and models the interaction between slip and GB sliding. Atomistic simulations are used to formulate the constitutive model for GB sliding and its interaction with incident slip. The deformation fields and structure of the GBs are obtained directly from experimental characterization and are faithfully reproduced as bicrystal systems for molecular dynamics simulations. The GBs are modeled as random-type (non-coincidence, asymmetrical) boundaries as observed from experimental data. The underlying atomistic-scale mechanism for pure sliding of random GBs was found to be analogous to fluid-flow. The interaction between incident slip and a sliding GB caused local increases in stress concentration, which further led to a momentary increase in the local sliding rate. The displacement profiles at the sliding GBs computed from the CP model with sliding accommodation are 38% more accurate than the baseline CP model as quantified by the mean squared error between the simulations and experiment. These results help improve the sophistication and accuracy of deformation modeling by including physics-based descriptions for GB sliding and its interaction with slip, eventually leading to more reliable predictions of micromechanical quantities.

Effect of strain and high temperature annealing on grain boundary characteristic distribution of compositionally complex Fe-Mn-Al-C-Cr steel

The optimization of the grain boundary of compositionally complex Fe-Mn-Al-C-Cr Steel was realized by low strain (≤5%) and annealing at 1100 ℃ for 30 min. The fraction of coincident site lattice (CSL) boundaries has reached 82.9%. Larger strain (≥10%) promoted the recrystallization of grains, leading to failure of the optimization of grain boundaries, and the grains presented a bimodal distribution. The stress mainly concentrated on random grain boundaries (RGBs) and twin boundaries, which made part of twin boundaries deviate from their ideal orientation. Low strain and annealing promoted the faceting-roughening transition to form incoherent twin grain boundaries with various morphologies. The incoherent twin boundaries also tended to the ideal orientation and were easier to migrate due to their higher energy, resulting in the formation of grain clusters with Σ3n orientation relationship. The two signs of realizing the optimization of grain boundaries were large-sized grain clusters and broken RGBs.

In situ scanning tunneling microscopy study of 2-mercaptobenzimidazole local inhibition effects on copper corrosion at grain boundary surface terminations

New insight on local inhibition effects of 2-mercaptobenzimidazole (MBI) on early stage intergranular corrosion of copper in hydrochloric acid solution is reported from in situ analysis at the nanometer scale and comparison with 2-mercaptobenzothiazole (MBT) effects in the same pre-adsorption and corrosion testing conditions. Macroscopic cyclic voltammetry analysis, including grains and grain boundary (GB) network, showed a passivation-like behavior in the Cu(I) oxidation range, specific to MBI since not observed with MBT and assigned to the anodic formation of a surface film of Cu(I)-MBI reaction products protecting against dissolution. Electrochemical scanning tunneling microscopy analysis revealed net intergranular dissolution, mitigated by the imperfect protection provided by the anodically formed MBI layer. It also showed local accumulation of reaction products in the GB surface regions, blocking preferential dissolution. For random GBs, blocking by local accumulation of reaction products was dominant, in agreement with the expected higher reactivity of these GBs generating more Cu(I) ions under anodic polarization and thus less efficiently protected by the anodically formed MBI layer. For Coincidence Site Lattice (CSL) boundaries, mitigated net dissolution was more frequently observed. Coherent twins showed equally efficient inhibition in the GB surface region than on adjacent grains. MBI inhibition was less efficient than MBT inhibition with more Cu(I) reaction products generated on the grains to form a surface film and their preferential local accumulation more frequently observed in the GB surface regions.

Local Inhibition by 2-mercaptobenzothiazole of Early Stage Intergranular Corrosion of Copper

Corrosion inhibition by 2-mercaptobenzothiazole (MBT) at the surface termination of various types of grain boundaries (GBs) was studied at the nanometer scale on microcrystalline copper in HCl acid solution using in situ electrochemical scanning tunneling microscopy (ECSTM). Macroscopic electrochemical analysis by cyclic voltammetry showed highly effective inhibition of Cu(I) active dissolution blocked by MBT pre-adsorption in a potential range of 0.15–0.2 V. ECSTM analysis of the initial stages of intergranular corrosion confirmed the mitigation of net intergranular dissolution by the pre-adsorbed MBT surface layer but also revealed the local accumulation of reaction products in the GB regions. For Coincidence Site Lattice boundaries other than coherent twins, intergranular dissolution, mitigated by the pre-adsorbed MBT layer, and protection by intergranular formation of a film of reaction products were observed. For random GBs, protection by reaction products was dominant, in agreement with their more reactive intrinsic character, generating more Cu(I) ions under anodic polarization and thus promoting the formation of a protective film of reaction products. Coherent twins did not show preferential intergranular reactivity compared to adjacent grains, indicating equally strong efficiency than on grains. These results bring new insight on how inhibition operates locally at various types of GBs.

Prediction of formation energies of large-scale disordered systems via active-learning-based executions ofab initiolocal-energy calculations: A case study on a Fe random grain boundary model with millions of atoms

We have developed a method that can analyze large random grain boundary (GB) models with the accuracy of density functional theory (DFT) calculations using active learning. It is assumed that the atomic energy is represented by the linear regression of the atomic structural descriptor. The atomic energy is obtained through DFT calculations using a small cell extracted from a huge GB model, called replica DFT atomic energy. The uncertainty reduction (UR) approach in active learning is used to efficiently collect the training data for the atomic energy. In this approach, atomic energy is not required to search for candidate points; therefore, sequential DFT calculations are not required. This approach is suitable for massively parallel computers that can execute a large number of jobs simultaneously. In this study, we demonstrate the prediction of the atomic energy of a Fe random GB model containing one million atoms using the UR approach, and we show that the prediction error decreases more rapidly compared with random sampling. We conclude that the UR approach with replica DFT atomic energy is useful for modeling huge GBs and will be essential for modeling other structural defects.

Role of Random and Coincidence Site Lattice Grain Boundaries in Liquid Metal Embrittlement of Iron (FCC)-Zn Couple

Liquid metal embrittlement (LME) has frequently been reported in various systems: Cu-Bi, Ni-Bi, Al-Ga, and Fe-Zn for more than 60 years. Although advances have been made in understanding the phenomenon, the role of grain boundary (GB) type and characteristics in LME has remained unclear. The present work shows that liquid metal penetration only occurs in random GBs, where its propagation path is a function of misorientation angle (θ) and stress component perpendicular to GB plane. In contrast, low-Σ coincidence site lattice (CSL) boundaries: Σ3 (θ = 60 deg) and Σ5 to 9 (~ θ = 40 deg) resist LME, even at the maximum stress component. Triple junctions of CSL and random GB block liquid metal penetration by modifying of the random GB misorientation angle. These findings provide insights to employ grain boundary engineering techniques to increase population of CSLs over random GBs and, hence, mitigate LME.