Boundary Complexion Transitions Research Articles

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%.

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.

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.

A model of grain boundary complexion transitions and grain growth in Yttria-doped alumina

In this work, we present a physically-parameterized microstructure evolution model for the Yttria-doped alumina system. Yttria-doped alumina is a well-known ceramic system which undergoes first-order phase-like transitions at grain boundaries, which can radically alter interface properties. The change in interfacial properties in turn can radically change microstructure outcomes during processing, including the induction of abnormal grain growth modes. In this work, we develop a simulation that evolves alumina microstructure as a function of yttria concentration and temperature. In the window studied, we achieve strong agreement with reviewed experimental results in identifying the windows for large grains, small grains, abnormal grain growth, and complexion transition kinetics (as measured by JMAK analysis). We then apply the model to study and demonstrate how the possible inclusion of second-phase particles or uneven solute distribution profiles will impact microstructure evolution. It is found that particles do not significantly affect abnormal grain growth in the window studied (but do lead to reduced grain size through pinning effects). It is found that even modest amounts of solute inhomogeneity will result in substantial changes in microstructure outcomes, frequently leading to clusters of abnormal grains. This model largely corroborates the expectations and hypotheses made from recent experimental studies in oxide-doped alumina systems. Further, it is found that there exists a peak transition fraction for the system at which abnormal grain size tends to be maximized.

A Model of Grain Boundary Complexion Transitions and Grain Growth in Yttria-Doped Alumina

In this work, we present a physically-parameterized microstructure evolution model for the Yttria-doped alumina system. Yttria-doped alumina is a well-known ceramic system which undergoes first-order phase-like transitions at grain boundaries, which can radically alter interface properties. The change in interfacial properties in turn can radically change microstructure outcomes during processing, including the induction of abnormal grain growth modes. In this work, we develop a simulation that evolves alumina microstructure as a function of yttria concentration and temperature. In the window studied, we achieve strong agreement with reviewed experimental results in identifying the windows for large grains, small grains, and abnormal grain growth. We then apply the model to study and demonstrate how the possible inclusion of second-phase particles or uneven solute distribution profiles will impact microstructure evolution. It is found that particles do not significantly affect abnormal grain growth in the window studied (but do lead to reduced grain size through pinning effects). It is found that even modest amounts of solute inhomogeneity will result in substantial changes in microstructure outcomes, frequently leading to clusters of abnormal grains. This model largely corroborates the expectations and hypotheses made from recent experimental studies in oxide-doped alumina systems.

Abnormal grain growth in the Potts model incorporating grain boundary complexion transitions that increase the mobility of individual boundaries

The Potts model of grain growth was adapted for the purpose of simulating abnormal grain growth (AGG) resulting from grain boundary complexion transitions. The transition in grain boundary structure between specific complexion types results in changes in properties. Where the transitions decrease energy and increase the mobility of boundaries, AGG occurs provided that such transitions predominantly occur via propagation to adjacent boundaries. Thus the model increases the mobility of selected boundaries on the basis of their adjacency to zero, one, or a multiplicity of boundaries that have already transitioned. The effect of transitions to a high mobility complexion was investigated separately from the effect of changes in energy. The influence of the frequency of complexion transitions with different adjacencies on the occurrence of AGG was explored. The simulations show how propagating complexion transitions can explain the AGG observed in certain ceramic systems.

Grain boundary complexions

Grain boundaries exhibit phase-like behavior in which their structure, chemistry and properties may change discontinuously at critical values of thermodynamic parameters such as temperature, pressure and chemical potential. Therefore, grain boundaries (and other interfaces such as surfaces and heterophase boundaries) can be treated as thermodynamically stable interfacial states. To differentiate these interfacial states from bulk phases, the term “complexion” has been introduced. A variety of terminology has been used to describe complexions and complexion transitions. In many cases, several terms exist that describe essentially the same phenomenon. We give an overview of complexion-related terminology, suggest a preferred nomenclature and discuss a classification framework that can be used to categorize complexions and complexion transitions. The field of grain boundary complexions has evolved rapidly in the past decade due to advances in experimental equipment – in particular, aberration-corrected transmission electron microscopy – and progress in computational simulation methods. Grain boundary complexion transitions are the root cause of a wide variety of materials phenomena – such as abnormal grain growth, grain boundary embrittlement and activated sintering – that have defied mechanistic explanation for years. In this overview, we review the history and theory of grain boundary complexion transitions, their role in materials processing and their effect on materials properties.

The Relationship between Grain Boundary Energy, Grain Boundary Complexion Transitions, and Grain Size in Ca-Doped Yttria

The thermal groove technique has been used to measure relative grain boundary energies in two 100 ppm Ca-doped yttria samples. The first has a normal grain size distribution and the boundaries have a bilayer of segregated Ca. In the second sample, there is a combination of large grains and small grains. The boundaries around the large grains are known to have an intergranular film. The results show that the relative energies of boundaries in the sample with normal grain growth and the boundaries around small grains far from larger grains in the second sample are similar. Also, boundaries surrounding the largest grains and small grains immediately adjacent to them have the same and significantly lower energies. The results indicate that grain boundaries with an intergranular film have a lower energy than those with bilayer segregation and that the intergranular film extends beyond the periphery of the largest grains, but not throughout the entire sample.

Grain boundary complexion transitions in WO3- and CuO-doped TiO2 bicrystals

Several grain boundary complexions (grain boundary interfacial phases) have been identified in TiO2 bicrystals by high-resolution transmission electron microscopy (TEM) and aberration-corrected scanning TEM (STEM). An intrinsic grain boundary with no apparent impurity segregation was observed in an undoped TiO2 bicrystal. In a WO3-doped TiO2 bicrystal, WO3 second-phase particles formed along the boundary, with a nominally clean, intrinsic-type grain boundary in between the particles. In a CuO-doped bicrystal, a remarkable series of three distinct grain boundary complexions with abrupt structural transitions was discovered coexisting at the grain boundary, and the existence of a fourth equilibrium complexion at the annealing temperature was implied. Thus, the WO3- and CuO-doped TiO2 bicrystals exhibit dramatically different solute partitioning behavior which can be understood in terms of the relative interphase boundary energies of these two systems. STEM–electron energy loss spectroscopy and energy-dispersive X-ray spectroscopy analysis of the nanoscale lens-shaped films of amorphous material in the CuO-doped TiO2 bicrystal demonstrated an excess of CuO, as expected, yet also revealed the unintentional presence of SiOx. The multiple grain boundary complexions in CuO-doped TiO2 offer an explanation for the CuO-enhanced grain growth and sintering of TiO2 that has been reported in the literature. Conversely, the intrinsic grain boundary complexion observed in WO3-doped TiO2 is consistent with previous work showing that WO3 has no effect on grain boundary mobility in TiO2. A phenomenological thermodynamic model is proposed to explain the physical origin of these observed grain boundary complexions and the abrupt, first-order complexion transitions that are believed to occur upon cooling of the CuO-doped TiO2 bicrystal.

Influence of interface energies on solute partitioning mechanisms in doped aluminas

The experiments described in this paper have been designed to understand how particular dopants in alumina (Ca, Mg, Si, and Y) affect microstructural development through the energetics of their associated precipitates. Specifically, the role of the interphase boundary energy and precipitation activation energy are considered to be in competition with grain boundary complexion (disorder) transitions for partitioning excess solute. The results reveal a relationship between the relative precipitation activation energy and the temperature at which grain boundary complexion transitions occur. The large differences in activation energy primarily derive from the interphase boundary energy. Precipitates that form lower interphase boundary energies tend to suppress complexion transitions, while systems that contain precipitates with high interphase boundary energies are more susceptible. Based on the findings, a new criterion for additive selection to control complexion transitions and abnormal grain growth is proposed that is based on interfacial energies between the host and precipitate.

Grain boundary plane distributions in aluminas evolving by normal and abnormal grain growth and displaying different complexions

Abstract The grain boundary character distributions of selected doped aluminas were measured from normal and abnormal populations. The relative energies of the A-, C-, and R-planes of undoped alumina were also measured. There is an inverse relationship between the population of grain boundaries and the relative energies of grain boundary planes in undoped alumina. This relationship is found to be qualitative for abnormal grains, whose interfacial anisotropy may be affected by kinetic factors. It is found that the relative grain boundary anisotropy correlates with the temperature dependence of grain boundary complexion transitions in a particular system that is prone to abnormal grain growth. However, there is no direct correlation between the total anisotropy of the grain boundary character distribution and that system's propensity to undergo a particular complexion transition. Therefore, anisotropy will significantly affect the microstructural evolution in systems that are prone to abnormal grain growth, but the magnitude of anisotropy is not a sufficient selection criterion for determining which systems will undergo abnormal grain growth.