Boundary Complexions Research Articles

Realizing Ultrahigh Near-Room-Temperature Thermoelectric Figure of Merit for N-Type Mg3(Sb,Bi)2 through Grain Boundary Complexion Engineering with Niobium.

Despite decades of extensive research on thermoelectric materials, Bi2Te3 alloys have dominated room-temperature applications. However, recent advancements have highlighted the potential of alternative candidates, notably Mg3Sb2-Mg3Bi2 alloys, for low- to mid-temperature ranges. This study optimizes the low-temperature composition of this alloy system through Nb addition (Mg3.2-xNbx(Sb0.3Bi0.7)1.996Te0.004), characterizing composition, microstructure, and transport properties. A high Mg3Bi2 content improves the band structure by increasing weighted mobility while enhancing the microstructure. Crucially, it suppresses detrimental grain boundary scattering effects for room-temperature applications. While grain boundary scattering suppression is typically achieved through grain growth, our study reveals that Nb addition significantly reduces grain boundary resistance without increasing grain size. This phenomenon is attributed to a grain boundary complexion transition, where Nb addition transforms the highly resistive Mg3Bi2-rich boundary complexion into a less resistive, metal-like interfacial phase. This marks the rare demonstration of chemistry noticeably affecting grain boundary interfacial electrical resistance in Mg3Sb2-Mg3Bi2. The results culminate in a remarkable advancement in zT, reaching 1.14 at 330 K. The device ZT is found to be 1.03 at 350 K, which further increases to 1.24 at 523 K and reaches a theoretical maximum device efficiency (ηmax) of 10.5% at 623 K, underscoring its competitive performance. These findings showcase the outstanding low-temperature performance of n-type Mg3Bi2-Mg3Sb2 alloys, rivaling Bi2Te3, and emphasize the critical need for continued exploration of complexion phase engineering to advance thermoelectric materials further.

Boron induced abnormal grain growth in alumina

In this work, hot-pressing of alumina in contact with hexagonal boron nitride or doped with boron carbide was conducted at 1500 °C for 30 min. After hot-pressing, abnormal grain growth induced by boron diffusion from these substances into alumina was detected, as clearly demonstrated with SEM, EDS, EBSD, and Raman spectroscopy. Grain boundary complexion transformations, solute drag, or another mechanism relating to interface-controlled grain boundary mobility are presumed to be the fundamental mechanism responsible for abnormal grain growth observed in this work.

An effective strategy to inhibit grain coarsening: Construction of multi-element co-segregated grain boundary complexion

An effective strategy to inhibit grain coarsening: Construction of multi-element co-segregated grain boundary complexion

Grain boundary complexion modification for interface stability in garnet based solid-state Li batteries

The garnet type solid-state electrolyte (SSE) encounters challenges related to poor interfacial contact with Li metal and dendrite penetration problem. This study addresses these issues by manipulating the surface property of garnet-based LLZTO (Li6.5La3Zr1.6Ta0.4O12) SSE. The manipulation is achieved by varying thickness of Al2O3 atomic layer deposition (ALD), followed by sintering. Research results show that the relative density, ionic conductivity, and hardness of LLZTO are improved while electronic conductivity is reduced due to the formation of multiple complexions at grain boundary (GB). The SSE pellets also demonstrate improved wettability with Li metal, leading to stable galvanostatic Li plating/stripping cycling with low polarization, which allows for batter battery performance than pristine one. The concept of modifying SSE through the grain boundary complexion modification by thin ALD coating for enhancing the dendrite tolerance with better electrochemical properties of SSE may open a new direction for solid state battery research.

Enhanced Radiation Damage Tolerance of Amorphous Interphase and Grain Boundary Complexions in Cu-Ta

Enhanced Radiation Damage Tolerance of Amorphous Interphase and Grain Boundary Complexions in Cu-Ta

Persistence of abnormal grain growth in the presence of grain boundary complexion transitions: Thermodynamic analysis and phase field modeling

An anomalous feature in polycrystalline grain growth in metals and ceramics is the rapid abnormal growth of a few grains relative to the surrounding matrix grains. In certain systems, this phenomenon is reported to be associated with the presence of first order phase transitions in the grain boundaries often referred to as complexion transitions. The fundamental question of how the growth advantage of abnormally growing grains persists in this context is not yet well understood. We present a thermodynamically consistent mechanism by which abnormal grain growth may occur. The presence of two complexion transitioned boundaries at a triple junction provides a driving force for partial wetting at the triple junction leading to the formation of a quadruple junction. The subsequent dissociation of the quadruple junction into two partial wetting triple junctions favors the persistence of abnormal grain growth. We incorporate this dissociation process into a multi-order parameter phase field model and demonstrate the occurrence of abnormal grain growth without the need for mobility advantage or additional driving forces. The results from simulations of abnormal grain growth capture experimentally observed microstructural features such as peninsular and island grains. Through a systematic study we show that the initial fraction of complexion boundaries plays a significant role in abnormal grain growth and that maximum abnormal grain growth is observed when the fraction of complexion boundaries is less than about 2%.

Local structural ordering determines the mechanical damage tolerance of amorphous grain boundary complexions

Amorphous grain boundary complexions act as toughening features within a microstructure because they can absorb dislocations more efficiently than traditional grain boundaries. This toughening effect should be a strong function of the local internal structure of the complexion, which has recently been shown to be determined by grain boundary crystallography. To test this hypothesis, molecular dynamics are used here to simulate dislocation absorption and damage nucleation for complexions with different distributions of structural short-range order. The complexion with a more disordered structure away from the dislocation absorption site is actually found to better resist crack nucleation, as damage tolerance requires delocalized deformation and the operation of shear-transformation zones through the complexion thickness. The more damage tolerant complexion accommodates plastic strain efficiently within the entire complexion, providing the key mechanistic insight that local patterning and asymmetry of structural short-range order controls the toughening effect of amorphous complexions.

Grain boundary complexions formed by chemical plating of Cu enhance the thermoelectric properties of Sn0.94Mn0.09Te

Grain boundaries (GBs) often lead to increased electrical resistivity due to the extra GB resistance. This restricts the improvement of thermoelectric performance by nanostructuring. We demonstrate that the electrical conductivity can be improved without sacrificing the Seebeck coefficient by chemically decorating GBs with Cu in SnTe-based compounds. Cu-rich GB complexions are formed by sintering Cu-decorated Sn0.94Mn0.09Te powders via electroless plating. We find that the electrical conductivity increases while remaining the Seebeck coefficient upon increasing the Cu content. This indicates that the effect of chemical plating Cu is to modify the GB properties rather than playing as dopants to tune the carrier concentration of the matrix. Moreover, these Cu-rich GB complexions significantly enhance the scattering of phonons at high temperatures. As a consequence, the ZT value is improved from 0.65 for the pristine Sn0.94Mn0.09Te to 1.05 at 876 K for the Cu-incorporated Sn0.94Mn0.09Te.

Grain incompatibility determines the local structure of amorphous grain boundary complexions

Amorphous grain boundary complexions lack long-range crystalline order but are not featureless, as distinct gradients in structural short-range order have been reported through their thickness. In this work, we test the hypothesis that the distribution of short-range order is determined by the confining crystals using atomistic simulations of both Cu-Zr bicrystals and a random polycrystal. Voronoi polyhedra with structures similar to that of perfect face-centered cubic serve as signatures of high structural order and are only found at the amorphous-crystalline transition regions. The density of the ordered structural motifs within a specific amorphous-crystalline transition region is found to not be directly determined by the orientation and symmetry of the grain which touches it, but rather by the incompatibility between the two confining grains. Ordered polyhedra density is found to be inversely related to grain incompatibility, meaning that large incompatibilities between the confining crystals lead to less order in the amorphous-crystalline transition region. The finding that the entire grain-film-grain system must be considered to understand local structure unequivocally demonstrates that amorphous complexions are not simply a collection of independent phases which happen to nucleate at a grain boundary. Rather, an amorphous grain boundary complexion is a single entity that finds a local equilibrium configuration.

Grain Boundary Complexions Enable a Simultaneous Optimization of Electron and Phonon Transport Leading to High‐Performance GeTe Thermoelectric Devices

AbstractGrain boundaries (GBs) form ubiquitous microstructures in polycrystalline materials which play a significant role in tuning the thermoelectric figure of merit (ZT). However, it is still unknown which types of GB features are beneficial for thermoelectrics due to the challenge of correlating complex GB microstructures with transport properties. Here, it is demonstrated that GB complexions formed by Ga segregation in GeTe‐based alloys can optimize electron and phonon transport simultaneously. The Ga‐rich complexions increase the power factor by reducing the GB resistivity with slightly improved Seebeck coefficients. Simultaneously, they lower the lattice thermal conductivity by strengthening the phonon scattering. In contrast, Ga2Te3 precipitates at GBs act as barriers to scatter both phonons and electrons and are thus unable to improve ZT. Tailoring GBs combined with the beneficial alloying effects of Sb and Pb enables a peak ZT of ≈2.1 at 773 K and an average ZT of 1.3 within 300–723 K for Ge0.78Ga0.01Pb0.1Sb0.07Te. The corresponding thermoelectric device fabricated using 18‐pair p‐n legs shows a power density of 1.29 W cm−2 at a temperature difference of 476 K. This work indicates that GB complexions can be a facile way to optimize electron and phonon transport, further advancing thermoelectric materials.

Why do compact grain boundary complexions prevail in rock-salt materials?

Over 40 years of studies of grain boundaries in ionic rock-salt materials have left the community divided. On one hand, numerical simulations systematically predict open, hollow structural units to be the ground state. On the other, most recent experiments report compact structures to be the norm. To reconcile modelling with experimental evidence, we investigate the stability of three high-angle symmetric tilt grain boundaries in magnesium oxide MgO with respect to the presence of charge-neutral vacancy pairs. We demonstrate that although open structural units are energetically the most favourable, they are easily destabilized by vacancies. It follows that open complexions can never be at equilibrium with the surrounding grains at finite temperature. On the contrary, compact structural units can accommodate a wide range of defects concentrations, and are much more resilient with respect to the absorption of vacancies. These results highlight the limitations of studies that consider only the ground state, and stress the importance of accounting for the presence of other defects when modelling grain boundaries in ionic materials.

New insights into the formation mechanism of zircon in a ZrO2–SiO2 nanocrystalline glass-ceramic: A TEM study

We have previously observed that doping of Ca ions was beneficial to the formation of zircon (ZrSiO4). It is well known that synthetic ZrSiO4 is typically formed via a solid-state reaction between ZrO2 and SiO2, in which the interfaces between the reactant and resultant play an important role. However, the interfaces are lacking detailed microstructural observation. This follow-up study aims at exploring the formation mechanism of ZrSiO4 by inspecting the interfaces at the nano and atomic scales with TEM techniques. Results demonstrated that ZrSiO4 was formed in the Ca-doped sample after sintering at 1200 °C, whereas, no ZrSiO4 was formed in the undoped sample even after sintering at 1230 °C. The Ca-doped sample consisted of a continuous ZrSiO4 matrix with dispersed ZrO2 nanocrystallites. Doping of Ca ions promoted the formation of ZrSiO4 by causing lattice distortion and oxygen vacancies in ZrO2 lattices. Thin amorphous grain boundary complexions were found between ZrO2 nanocrystallites and between ZrO2 and ZrSiO4 crystallites. These amorphous complexions acted as reaction sites and an intermediate metastable state for the solid-state reaction. A detailed formation mechanism of ZrSiO4 at the nanometer scale and atomic scale has been proposed.

Synergistic effect of binary fluoride sintering additives on the properties of silicon nitride ceramics

A variety of combinations of YF3 and MgF2 were used as sintering aids in the fabrication of Si3N4 ceramics via gas pressure sintering (GPS). The synergistic effects of YF3 and MgF2 on the liquid viscosity, mechanical properties, thermal conductivities, and grain growth kinetics of the Si3N4 ceramics were investigated. The results showed that appropriately adjusting the YF3/MgF2 ratio could decrease liquid viscosity, reducing the diffusion energy barrier of the solute atom and promoting mass transfer. Meanwhile, the chemical bonding strength in the grain boundary complexions formed by the metal cations also influenced grain boundary migration. Samples doped with 4 mol% YF3 and 2 mol% MgF2 achieved the lowest grain growth exponent (n = 2.9) and growth activation energy (Q = 616.7 ± 16.5 kJ mol−1) as well as the highest thermal conductivity (83 W m−1 K−1) and fracture toughness (8.82 ± 0.13 MPa m1/2).

Grain boundary segregation in Si-doped B-based ceramics and its effect on grain boundary cohesion

Boron carbide and boron suboxide are attractive for their low densities and ultrahigh hardness values, yet they exhibit poor fracture resistance. Strategies to improve mechanical performance aim to control bulk microstructures and properties by incorporating Si-based additives. A related approach to toughen boron carbide is tailoring the phase-like states of grain boundaries by applying the concept of grain boundary complexion engineering. This work directly investigates the potential of grain boundary complexion engineering to improve fracture resistance by systematically evaluating grain boundary segregation behavior of a polycrystalline silicon hexaboride / boron carbide diffusion couple using aberration-corrected scanning transmission electron microscopy and ζ-factor microanalysis. A main result was that all grain boundaries in the diffusion couple exhibited Si segregation that, depending on the bulk Si concentration, approached up to 3 monolayers of coverage, thereby resulting in nanolayer complexions (oftentimes known as intergranular films). Furthermore, upon analyzing 110 distinct grain boundaries throughout the diffusion zone and an impurity boron suboxide region, free energies of Si segregation in boron carbide and boron suboxide were experimentally determined using the Brunauer, Emmett and Teller (BET) multilayer grain boundary segregation theory. Subsequently, changes in grain boundary energy due to Si segregation were quantified and a maximum energy reduction of 51% and 81% were observed in boron carbide and boron suboxide, respectively, which led to decreases in works of adhesion of 18% and 17%, respectively. In summary, this work uncovers grain boundary processing-structure-property relationships that can be used to improve the fracture resistance in icosahedral boron-based ceramics.

The Importance of Surface Adsorbates in Solution-Processed Thermoelectric Materials: The Case of SnSe.

Solution synthesis of particles emerges as an alternative to prepare thermoelectric materials with less demanding processing conditions than conventional solid-state synthetic methods. However, solution synthesis generally involves the presence of additional molecules or ions belonging to the precursors or added to enable solubility and/or regulate nucleation and growth. These molecules or ions can end up in the particles as surface adsorbates and interfere in the material properties. This work demonstrates that ionic adsorbates, in particular Na+ ions, are electrostatically adsorbed in SnSe particles synthesized in water and play a crucial role not only in directing the material nano/microstructure but also in determining the transport properties of the consolidated material. In dense pellets prepared by sintering SnSe particles, Na remains within the crystal lattice as dopant, in dislocations, precipitates, and forming grain boundary complexions. These results highlight the importance of considering all the possible unintentional impurities to establish proper structure-property relationships and control material properties in solution-processed thermoelectric materials.

Segregation competition and complexion coexistence within a polycrystalline grain boundary network

Interfacial segregation can stabilize grain structures and even lead to grain boundary complexion transitions. However, understanding of the complexity of such phenomena in polycrystalline materials is limited, as most studies focus on bicrystal geometries. In this work, we investigate interfacial segregation and subsequent complexion transitions in polycrystalline Cu-Zr alloys using hybrid Monte Carlo/molecular dynamics simulations. No significant change in the grain size or structure is observed upon Zr dopant addition to a pure Cu polycrystal at moderate temperature, where grain boundary segregation is the dominant behavior. Segregation within the boundary network is inhomogeneous, with some boundaries having local concentrations that are an order of magnitude larger than the global value and others having almost no segregation, and changes to physical parameters such as boundary free volume and energy are found to correlate with dopant concentration. Further, another alloy sample is investigated at a higher temperature to probe the occurrence of widespread transitions in interfacial structure, where a significant fraction of the originally ordered boundaries transition to amorphous complexions, demonstrating the coexistence of multiple complexion types, each with their own distribution of boundary chemical composition. Overall, this work highlights that interfacial segregation and complexion structure can be diverse in a polycrystalline network. The findings shown here complement existing computational and experimental studies of individual interfaces and help pave the way for unraveling the complexity of interfacial structure in realistic microstructures.

Discovery of electrochemically induced grain boundary transitions

Electric fields and currents, which are used in innovative materials processing and electrochemical energy conversion, can often alter microstructures in unexpected ways. However, little is known about the underlying mechanisms. Using ZnO-Bi2O3 as a model system, this study uncovers how an applied electric current can change the microstructural evolution through an electrochemically induced grain boundary transition. By combining aberration-corrected electron microscopy, photoluminescence spectroscopy, first-principles calculations, a generalizable thermodynamic model, and ab initio molecular dynamics, this study reveals that electrochemical reduction can cause a grain boundary disorder-to-order transition to markedly increase grain boundary diffusivities and mobilities. Consequently, abruptly enhanced or abnormal grain growth takes place. These findings advance our fundamental knowledge of grain boundary complexion (phase-like) transitions and electric field effects on microstructural stability and evolution, with broad scientific and technological impacts. A new method to tailor the grain boundary structures and properties, as well as the microstructures, electrochemically can also be envisioned.

Effect of Eu‐doping and grain boundary plane on complexion transitions in MgAl2O4

AbstractEu‐doped MgAl2O4 has been used to evaluate the kinetics of equilibrium grain boundary transformations, otherwise known as complexion transitions, by monitoring abnormal grain growth induced the nucleation of highly mobile complexions. The assumption in prior works was that abnormal grain growth can be charted using time‐temperature‐transformation (TTT) diagrams to reflect the complexion transition nucleation and growth kinetics. A model depending on doping concentration, grain size, and abnormal area fraction has also been recently developed to estimate excess grain boundary coverage, and thereby predict complexion types depending on microstructural descriptors. While useful, the grain boundary excess model has not been validated using atomic‐resolution characterization. This work aimed to directly validate the grain boundary excess model and complexion TTT diagrams by applying aberration‐corrected electron microscopy to characterize grain boundary structures and compositions (i.e., complexions) in Eu‐doped MgAl2O4. Eu doping concentrations of 100 ppm and 500 ppm were produced and bulk samples were annealed at 1600°C for different times. Forty‐five distinct grain boundaries were characterized. Overall, at least five grain boundary complexion types were identified and the grain boundary excess model was validated. Interpretability of the grain boundary excess model and correlations between grain boundary structures and compositions are discussed.

Neural Network Based Modeling of Grain Boundary Complexions Localized in Simple Symmetric Tilt Boundaries Σ3 (111) and Σ5 (210)

A method is proposed for the neural network based analysis of the existence and stability of grain boundary complexions formed at high-symmetry tilt boundaries Σ3 (111) and Σ5 (210) in a polycrystalline Ni(Bi) solid solution. This method is based on the use of reference interparticle interaction potentials constructed within the framework of the density functional theory in combination with the structural capabilities of an artificial two-level self-learning neural network. The absolute error in determining potential energy by the neurosystem analysis is 0.012 eV/atom. The values of the formation enthalpy of grain boundary complexions for Σ3 and Σ5 boundaries are in rather good agreement with the published results of simulating this system and experimental data.

Grain Boundary Complexion Transitions

Grain boundaries can undergo phase-like transitions, called complexion transitions, in which their structure, composition, and properties change discontinuously as temperature, bulk composition, and other parameters are varied. Grain boundary complexion transitions can lead to rapid changes in the macroscopic properties of polycrystalline metals and ceramics and are responsible for a variety of materials phenomena as diverse as activated sintering and liquid-metal embrittlement. The property changes caused by grain boundary complexion transitions can be beneficial or detrimental. Grain boundary complexion engineering exploits beneficial complexion transitions to improve the processing, properties, and performance of materials. Here, we review the thermodynamic fundamentals of grain boundary complexion transitions, highlight the strongest experimental and computationalevidence for these transitions, clarify a number of important misconceptions, discuss the advantages of grain boundary complexion engineering, and summarize existing research challenges.