Boundary Chemistry Research Articles

The Energetics and Topology of Grain Boundaries in Magnesium: An Ab Initio Study

First principles calculations were carried out on six different grain boundaries with complex, non-symmetrical, crystallography’s. Solute species (Gd and Zn) were placed in multiple locations to investigate their effect on the boundary energetics. The grain boundaries were found to have an intrinsic grain boundary energy, and this energy was not markedly affected by the solute concentration at the boundary. However, the work of separation (WSEP) was very sensitive to grain boundary chemistry. Boundaries of higher disorder were found to be more sensitive to boundary chemistry and showed higher values of WSEP and in the case of Gd, were more sensitive to solute concentration at the boundary. No correlation between the boundary behaviour and crystallography could be found, apart from the over-riding conclusion that all six boundaries showed markedly different behaviours, and the effect of solute on each were unique.

Heterointerface and grain boundary energies, and their influence on microstructure in multiphase ceramics

Heterointerface energy measurements for multiphase systems are rarely reported in the scientific literature in contrast to grain boundary energies for single phase systems. Hence, thermal groove dimensions on the surfaces of single-phase (YSZ, Al2O3, MgAl2O4), two-phase (YSZ/MgAl2O4, YSZ/Al2O3), and three-phase (YSZ/MgAl2O4/Al2O3) ceramics were measured using atomic force microscopy to calculate relative energies for six different types of interfaces. Average grain boundary and interfacial energies were estimated from relative values calculated using previously published surface energies. Our results show that relative areas of interfaces in a multiphase composite are governed by relative interface energies. We show that Al2O3-Al2O3 homointerfaces occur less frequently in the multiphase systems studied, attributed to their higher grain boundary energies compared to YSZ-YSZ and MgAl2O4-MgAl2O4 boundaries. Using the complex three-phase ceramic system as a model, we also show that heterointerface energies are intermediate between the grain boundary energies of each of the two associated phases. Grain boundary and heterointerface energies for any specific type of boundary were similar for single phases versus multiphases, but the influence of grain boundary chemistry variations is reflected in the energy distribution. Our findings contribute novel insights on grain boundary and heterointerface energies that can inform materials design due to their strong influences on microstructural evolution.

Multi-principal element grain boundaries: Stabilizing nanocrystalline grains with thick amorphous complexions

Amorphous complexions have recently been demonstrated to simultaneously enhance the ductility and stability of certain nanocrystalline alloys. In this study, three quinary alloys (Cu–Zr–Hf–Mo–Nb, Cu–Zr–Hf–Nb–Ti, and Cu–Zr–Hf–Mo–W) are studied to test the hypothesis that increasing the chemical complexity of the grain boundaries will result in thicker amorphous complexions and further stabilize a nanocrystalline microstructure. Significant boundary segregation of Zr, Nb, and Ti is observed in the Cu–Zr–Hf–Nb–Ti alloy, which creates a quaternary interfacial composition that limits average grain size to 63 nm even after 1 week at ~ 97% of the melting temperature. This high level of thermal stability is attributed to the complex grain boundary chemistry and amorphous structure resulting from multi-component segregation. High-resolution transmission electron microscopy reveals that the increased chemical complexity of the grain boundary region in the Cu–Zr–Hf–Nb–Ti alloy results in an average amorphous complexion thickness of 2.44 nm, approximately 44% and 32% thicker than amorphous complexions previously observed in Cu–Zr and Cu–Zr–Hf alloys.Graphical abstract

Critical Current Density Limitation of LLZO Solid Electrolyte: Microstructure vs Interface

Al-doped Li7La3Zr2O12 (LLZO) solid electrolyte is a promising candidate for all-solid-state lithium battery (ASSB) due to its high ionic conductivity and stability against lithium metal. Dense LLZO pellets were prepared by high-temperature sintering and a Li3BO3 melting agent was used to control the microstructure (grain size and grain boundary chemistry). An ionic conductivity of 0.49 mS·cm−1 was measured at room temperature. The LLZO/Li interface was modified by introducing an aluminum layer. The impact of the microstructure of LLZO ceramics and the chemistry of the LLZO/Li interface were discussed by measuring the critical current density (CCD). Even though secondary phases at the grain boundary lead to an increase of the electronic conductivity, no significant influence of the microstructure on the CCD value (50 μA·cm−2) has been established. The low CCD value has been improved by forming an Al-Li alloy interlayer at the LLZO/Li interface, due to a better homogenization of the Li current at the interface. In parallel, the applied pressure (0.09 MPa vs. 0.4 MPa) has been studied and did impact the CCD. A value of 0.35 μA·cm−2 was measured. These results highlight the conditions needed for keeping a good electrolyte/Li interface during the cycling of a solid state battery.

Prediction of grain boundary chemistry in multicomponent Mo alloys with coupled precipitation and segregation kinetics simulations

Simulations are carried out to predict the amount of dissolved solute contents in multi-component Mo-based alloys containing Hf, Ti, C and O during and after a model thermo-mechanical treatment. The results are used to model the amounts of C, O and Hf in grain boundaries after heat treatment with concurrent precipitation in the corresponding alloys and to correlate this to measured atom probe tomography data of grain boundary enrichment. Our unique combinatory approach that considers precipitation and segregation at the same time allows for successful prediction of grain boundary enrichment.

Emergence of near-boundary segregation zones in face-centered cubic multiprincipal element alloys

Grain boundaries have been shown to dramatically influence the behavior of relatively simple materials such as monatomic metals and binary alloys. The increased chemical complexity associated with multiprincipal element alloys is hypothesized to lead to unique grain boundary phenomena. To explore the relationship between grain boundary structure and chemistry in these materials, hybrid molecular dynamics/Monte Carlo simulations of a faceted $\mathrm{\ensuremath{\Sigma}}11$ $\ensuremath{\langle}110\ensuremath{\rangle}$ tilt boundary, chosen to sample both high- and low-energy boundary configurations, are performed in face-centered cubic (fcc) CrFeCoNiCu and CrFeCoNi equiatomic alloys. Unexpected enrichment of Fe is discovered in the fcc regions adjacent to the interface and found to be correlated with a structurally distinct region of reduced atomic volume. Comparison with the boundary of the same type in monatomic Cu demonstrates that altered near-boundary regions exist in simpler systems as well, with the chemical complexity of the multiprincipal element alloys highlighting its existence and importance.

Aluminum depletion induced by co-segregation of carbon and boron in a bcc-iron grain boundary

The local variation of grain boundary atomic structure and chemistry caused by segregation of impurities influences the macroscopic properties of polycrystalline materials. Here, the effect of co-segregation of carbon and boron on the depletion of aluminum at a Σ5 (3 1 0 )[0 0 1] tilt grain boundary in a α − Fe-4 at%Al bicrystal is studied by combining atomic resolution scanning transmission electron microscopy, atom probe tomography and density functional theory calculations. The atomic grain boundary structural units mostly resemble kite-type motifs and the structure appears disrupted by atomic scale defects. Atom probe tomography reveals that carbon and boron impurities are co-segregating to the grain boundary reaching levels of >1.5 at%, whereas aluminum is locally depleted by approx. 2 at.%. First-principles calculations indicate that carbon and boron exhibit the strongest segregation tendency and their repulsive interaction with aluminum promotes its depletion from the grain boundary. It is also predicted that substitutional segregation of boron atoms may contribute to local distortions of the kite-type structural units. These results suggest that the co-segregation and interaction of interstitial impurities with substitutional solutes strongly influences grain boundary composition and with this the properties of the interface.

Grain boundary segregation in Ni-base alloys: A combined atom probe tomography and first principles study

Grain boundary engineering (GBE) plays an important role in the design of new polycrystalline materials with enhanced mechanical properties. This approach has been shown to be very effective in design of Ni-base alloys, where grain boundary segregation is expected to play a central role in defining their mechanical behavior. In the present work, we apply a powerful combination of advanced experimental and theoretical methods to reveal the grain boundary chemistry of the 725 Ni-base alloy at the atomic level. The methods of investigation comprise atom probe tomography (APT) measurements and density functional theory (DFT) calculations. We also propose a way to cross-validate DFT and APT results in a DFT-based model approach for evaluation of the interfacial excess as a function of the heat treatment history of the material and its chemistry. Both theoretical and experimental methods are applied to a detailed analysis of the GB chemistry of three modifications of the 725 alloy and the results of this investigation are presented and discussed in detail.

Barium titanate-based thermistors: Past achievements, state of the art, and future perspectives

Barium titanate materials displaying a positive temperature coefficient of resistivity are ubiquitously employed as thermistors in electrical current and voltage control systems, as well as in gas and thermal sensing applications. The positive temperature coefficient of resistivity effect is widely accepted to be a grain boundary-based phenomenon, although detailed studies on grain boundary structure and chemistry, and their influence on the resulting electrical properties, are seriously lacking. Tailoring of the positive temperature coefficient of resistivity electrical characteristics, for specific high-value applications, will require improved understanding and control over grain boundary phenomenon. A comprehensive overview of the development of barium titanate-based positive temperature coefficient of resistivity ceramics is initially presented. We then advance to a discussion on emerging grain boundary characterization techniques, specifically, a stereographic analysis of electron backscatter diffraction data that could assist in enhancing control over BaTiO3 defect chemistry and microstructure, through characterization and subsequent manipulation of the population of grain boundary types. These techniques have great potential for increasing the understanding of the delicate interplay between processing conditions, chemistry, microstructure, and functional electrical properties, and are relevant to the development of advanced, high-performance ceramics and electroceramics in general. Contemporary advancements in the field, such as lead-free positive temperature coefficient of resistivity effect materials and multilayer miniaturized systems based on hypostoichiometric barium compositions, are reviewed. Finally, perspectives on future lines of thermistor research, with a focus on the energy sector, are presented including applications in gas separation and chemical sensing.

Resolving atomic-scale phase transformation and oxygen loss mechanism in ultrahigh-nickel layered cathodes for cobalt-free lithium-ion batteries

Summary Doped LiNiO2 has recently become one of the most promising cathode materials for its high specific energy, long cycle life, and reduced cobalt content. Despite this, the degradation mechanism of LiNiO2 and its derivatives still remains elusive. Here, by combining in situ electron microscopy and first-principles calculations, we elucidate the atomic-level chemomechanical degradation pathway of LiNiO2-derived cathodes. We uncover that the O1 phase formed at high voltages acts as a preferential site for rock-salt transformation via a two-step pathway involving cation mixing and shear along (003) planes. Moreover, electron tomography reveals that planar cracks nucleated simultaneously from particle interior and surface propagate along the [100] direction on (003) planes, accompanied by concurrent structural degradation in a discrete manner. Our results provide an in-depth understanding of the degradation mechanism of LiNiO2-derived cathodes, pointing out the concept that suppressing the O1 phase and oxygen loss is key to stabilizing LiNiO2 for developing next-generation high-energy cathode materials.

Critical cooling rates for amorphous-to-ordered complexion transitions in Cu-rich nanocrystalline alloys

Amorphous complexions in nanocrystalline metals have the potential to improve mechanical properties and radiation tolerance, as well as resistance to grain growth. In this study, the stability of amorphous complexions in binary and ternary Cu-based alloys is investigated by observing the effect of cooling rate from high temperature on the occurrence of amorphous-to-ordered complexion transitions. Bulk Cu-Zr and Cu-Zr-Hf alloy samples were annealed to induce boundary premelting and then quenched through a procedure that induces a gradient of local cooling rate through the sample height. Amorphous complexion thickness distributions were found to be invariant to local cooling rate in the Cu-Zr-Hf alloy, demonstrating enhanced stability of the amorphous complexion structure compared to the Cu-Zr alloy, which had thinner amorphous complexions in the regions that were slowly cooled. The experimental results are used to construct time-temperature-transformation diagrams for the amorphous-to-ordered complexion transition in both the binary and ternary alloys, enabling a deeper understanding of the influence of cooling rate and grain boundary chemistry on complexion transitions. The critical cooling rate necessary to avoid complexion transitions in the ternary alloy is found to be at least three orders of magnitude slower than that for the binary alloy.

Reductions in nitrogen oxides over the Netherlands between 2005 and 2018 observed from space and on the ground: Decreasing emissions and increasing O3 indicate changing NOx chemistry

Satellite measurements of tropospheric NO2 columns are valuable for monitoring long-term changes in air quality. However, direct linkage of satellite-derived NO2 trends with changes in underlying NOx emissions and NOx surface concentrations is complicated by the contribution of background NO2 to the column, by changes in the chemical regime wherein emissions take place, and by data sampling differences. Here we study the 2005–2018 changes in nitrogen oxides concentrations over the polluted Netherlands. We use the QA4ECV OMI NO2 retrievals, RIVM surface measurements of NO, NO2, and O3, wet deposition fluxes of nitrate, and NOx emissions reported in two European inventories (EMEP and TNO-MACC-III). We interpret the observed changes in concentrations with simulations by CLASS, a box model accounting for boundary layer dynamics and chemistry. Nationally averaged, OMI column NO2 and RIVM surface NO2 concentrations are reduced by 30% and 32% respectively between 2005 and 2018. This is in line with Dutch national NOx emissions from the TNO-MACC-III and EMEP inventories showing decreases of 32%–39%, respectively, between 2005 and 2018. There is no indication that the decrease in NO2 concentrations slows down after 2010. The observed reductions in nitrogen oxides differ between winter and summer and turn out to be modulated by ozone chemistry. The RIVM surface measurements show a stronger reduction in NOx than in NO2, accompanied by an increase in O3 of 4–6 ppbv, which is due to diminished NO-titration following the lower NOx emissions, especially in winter. CLASS simulations confirm that daytime O3 increases have shifted the NO–NO2 equilibrium more towards NO2, explaining the weaker reductions in NO2 (−30%) than in NOx (−40%) concentrations over time. The O3 increases occur both during day and during night, and have likely shortened the NOx lifetimes both in summer (via faster OH + NO2+M during daytime) and in winter (via faster nighttime N2O5 formation and subsequent hydrolysis). Our findings suggest a reduction in anthropogenic NOx emissions of approximately 30% in the southern part of the Netherlands, and propose that interpreting satellite NO2 trends as a proxy for trends in NOx emissions is well-possible over a high-NOx region, but requires careful analysis in terms of changes in the chemical regimes and NOx lifetime.

Correlations of grain boundary segregation to sintering techniques in a three-phase ceramic

The effects of using different sintering techniques (conventional, flash and spark plasma sintering) on grain boundary segregation were investigated in a 3-phase polycrystalline ceramic containing cubic 8 mol% Y2O3 stabilized ZrO2 (YSZ), α-Al2O3 and MgAl2O4. Six types of interfaces for each sintered sample were analyzed for grain boundary chemistry. Using aberration-corrected STEM and EDS, we show Al segregation at YSZ-YSZ boundaries, and Y/Zr segregation at Al2O3-Al2O3, MgAl2O4-MgAl2O4 and MgAl2O4-Al2O3 boundaries. YSZ-MgAl2O4 and YSZ-Al2O3 heterointerfaces, in contrast, do not show elemental segregation. Our results show that the type of segregation at different boundaries does not change with different sintering processes, indicating that elemental segregation mainly depends on initial sample composition, although the amount of segregation can vary. Quantitative analyses reveal that spark plasma sintering (950°C for 5 min, 100 MPa) results in relatively higher average segregation at grain boundaries and heterointerfaces compared to conventional sintering (1550°C for 10 h), suggesting that low temperatures result in higher grain boundary segregation. The average segregation concentrations at the grain boundaries of our flash sintered sample (estimated to reach 1700°C for 6 s) were found to be consistently similar to long-annealed spark-plasma sintered sample (1350°C for 20 h), suggesting that very high temperatures reached during flash process can achieve similar segregation concentrations compared to a SPS sample annealed for several hours at lower temperature. The presence of other phases in multi-phase systems can modify the grain boundary chemistry and segregation compared to segregation in single-phase ceramics.

Radiation-induced segregation in a ceramic.

Radiation-induced segregation is well known in metals, but has been rarely studied in ceramics. We discover that radiation can induce notable segregation of one of the constituent elements to grain boundaries in a ceramic, despite the fact that the ceramic forms a line compound and therefore has a strong thermodynamic driving force to resist off-stoichiometry. Specifically, irradiation of silicon carbide at 300 °C leads to carbon enrichment near grain boundaries, whereas the enrichment diminishes for irradiation at 600 °C. The temperature dependence of this radiation-induced segregation is different from that shown in metallic systems. Using an ab initio informed rate theory model, we demonstrate that this difference is introduced by the unique defect energy landscapes present in the covalent system. Additionally, we discover that grain boundaries in unirradiated silicon carbide grown by chemical vapour deposition are intrinsically carbon-depleted. The inherent grain boundary chemistry and its evolution under radiation are both critical for understanding the many properties of ceramics associated with grain boundaries.

Visualizing Phase Boundaries with Electrogenerated Chemiluminescence.

Reactivity at phase boundaries is central to many areas of chemistry, from synthesis to heterogeneous catalysis. New tools are necessary to gain a more detailed understanding of processes occurring at these boundaries. We describe a series of experiments to visualize phase boundaries using electrogenerated chemiluminescence (ECL) on glassy carbon electrodes. By taking advantage of the solubilities of the ECL luminophore and the coreactant in different liquid phases, we demonstrate that the interface of various phases (i.e., the boundaries formed between a water microdroplet, 1,2-dichloroethane, and a glassy carbon electrode and the boundaries formed between an oxygen bubble, water, and a glassy carbon electrode) can be evaluated. We measured microdroplet contact radii, the three-phase boundary thickness, and growth dynamics of electrogenerated O2 bubbles. These experimental tools and the fundamental knowledge they yield will find applications in biology, nanoscience, synthesis, and energy storage and conversion, where understanding phase boundary chemistry is essential.

Mechanical properties of stabilized nanocrystalline FCC metals

In this perspective, recent advances and current research challenges concerning the mechanical properties of stabilized nanocrystalline face-centered cubic (FCC) metals are discussed. First, a brief review of key experiments and modeling efforts over the last two decades is provided, with a focus on elucidating the mechanisms associated with plastic yield, hardening, and microstructure stabilization in nanocrystalline metals. This prior work has provided an understanding of the transition between dislocation-based and grain boundary-mediated mechanisms in plasticity and has identified several strategies to mitigate temperature or stress driven grain growth. Yet, the consequence of various stabilization methods on mechanical properties is not well understood. Future research challenges are presented in order to address this scientific gap, most critically the need to include grain boundary chemistry or grain boundary phases resulting from stabilization methods in new mechanistic theories for mechanical properties of nanocrystalline FCC metals.

Strengthening mechanisms in an ultrafine-grained Al[sbnd]Zn[sbnd]Mg[sbnd]Cu alloy processed by high pressure torsion at different temperatures

The microstructures of an AlZnMgCu alloy processed by high pressure torsion at room temperature and 200 °C were characterized by transmission Kikuchi diffraction and atom probe tomography. Hardening effects of different microstructural features including grain boundaries, dislocations and solute nanostructures were quantitatively calculated using existing models. Compared to the samples processed at room temperature, the samples deformed at 200 °C were of relative larger grain sizes, a lower dislocation density and more significant phase decomposition. Thus, the primary hardening effects, i.e. grain boundary hardening, dislocation hardening and cluster hardening subside at the elevated deformation temperature. Nevertheless, significant segregation of Mg and Cu formed at grain boundaries during deformation at 200 °C, which provides a remarkable hardening effect. The results revealed the importance of grain boundary chemistry on the mechanical strength of the ultrafine-grained materials.

Tailoring the Grain Boundary Chemistry of Polymeric Carbon Nitride for Enhanced Solar Hydrogen Production and CO2 Reduction.

Photocatalytic water splitting is a promising and clean way to mimic plant photosynthesis in a sustainable manner. Improvements of the quantum efficiency and optical absorption in the relevant range are necessary steps to approach practicality. Herein, we reported that these issues can be readily addressed when 5-aminotetrazole, a monomer with high nitrogen content, is used for the synthesis of carbon nitride. The molten salt mixture NaCl/KCl is used as a high-temperature solvent to tailor the grain boundary structure and chemistry. Visible light quantum efficiency for H2 production of 0.65 could be obtained in the presence of K2 HPO4 as a double layer modifier. This value is very high, considering that this number depends on light to charge couple conversion, charge localization, as well as a successful oxidation and reduction reaction.

Tailoring the Grain Boundary Chemistry of Polymeric Carbon Nitride for Enhanced Solar Hydrogen Production and CO2 Reduction

AbstractPhotocatalytic water splitting is a promising and clean way to mimic plant photosynthesis in a sustainable manner. Improvements of the quantum efficiency and optical absorption in the relevant range are necessary steps to approach practicality. Herein, we reported that these issues can be readily addressed when 5‐aminotetrazole, a monomer with high nitrogen content, is used for the synthesis of carbon nitride. The molten salt mixture NaCl/KCl is used as a high‐temperature solvent to tailor the grain boundary structure and chemistry. Visible light quantum efficiency for H2 production of 0.65 could be obtained in the presence of K2HPO4 as a double layer modifier. This value is very high, considering that this number depends on light to charge couple conversion, charge localization, as well as a successful oxidation and reduction reaction.

The Significance of Entropy in Grain Boundary Segregation.

The role of entropy in materials science is demonstrated in this report in order to establish its importance for the example of solute segregation at the grain boundaries of bcc iron. We show that substantial differences in grain boundary chemistry arise if their composition is calculated with or without consideration of the entropic term. Another example which clearly documents the necessity of implementing the entropic term in materials science is the enthalpy-entropy compensation effect. Entropy also plays a decisive role in the anisotropy of grain boundary segregation and in interface characterization. The consequences of the ambiguous determination of grain boundary segregation on the prediction of materials behavior are also briefly discussed. All the mentioned examples prove the importance of entropy in the quantification of grain boundary segregation and consequently of other materials properties.