The Electronic Structure of Pristine and Doped (100) Tilt Grain Boundaries in SrTiO3

To understand the electronic properties of doped grain boundaries, we reviewed the atomic scale techniques currently available to study the electronic structure at pristine SrTiO₃ grain boundaries. The knowledge gained from the pristine boundaries is used to interpret experimental and theoretical results from a Mn doped 5 SrTiO₃ grain boundaries. Mn atoms are shown to preferentially substitute at specific Ti sites at the grain boundary core. Furthermore, the formal oxidation state of the Mn atoms at the grain boundary core was found to be reduced compared to the Mn atoms substituting for Ti in the bulk. This change of valence did not, however, significantly affect the atomic structure of the grain boundary, as determined by Z-contrast imaging and electron energy-loss spectroscopy, which revealed similar fine-structure features at both the doped and pristine grain boundary. We conclude, therefore, that composition and atomic structure have different effects on the local electronic structure and should be treated separately in any segregation and electrical conductivity models for grain boundaries.     

Grain Boundary Migration in Fe-3wt.%Si Alloys

The studies of three different laboratories on grain boundary migration in Fe-3wt.%Si alloys are presented. In all cases bicrystal techniques employing capillarity as driving force were used. [100] tilt boundaries were studied in the temperature range from 1223 K to 1373 K, and [110] tilt boundaries in the range from 1220 K to 1625 K. Proportionality between grain boundary velocity and driving force was confirmed. All data fulfil a linear relation between activation enthalpies and logarithms of the pre-exponential factors, corresponding to a compensation temperature of 1386 K where all boundaries theoretically should possess the same mobility. A considerably lower activation enthalpy was found in one case for an asymmetrical grain boundary compared to the symmetrical boundary of the same misorientation. High values of activation enthalpy of migration were found for special [100] boundaries compared to general ones although an opposite tendency was also observed for [100] boundaries.     

Criteria for the Occurrence of the Diffusion-Induced Grain Boundary Migration

Recent experimental data on diffusion-induced grain boundary migration (DIGM) are reviewed. For the case of the coherency strain driving force, quantitative criteria for the occurrence of DIGM are suggested, which establish the relationship between the net driving force for grain boundary migration, the diffusivity in the vicinity of the grain boundary, the enthalpy of the grain boundary segregation, the misfit parameter for the solute atoms in the matrix and the solubility of the diffusing element in the matrix. It is shown that an upper limit for the grain boundary velocity during DIGM exists due to the solute drag effect.     

The effect of segregated transition metal ions on the grain boundary resistivity of gadolinium doped ceria: Alteration of the space charge potential

The effect of segregated transition metals on the grain boundary resistivity of 1 mol% Gd-doped ceria has been investigated. The main focus of interest is whether the space charge potential that causes the blocking effect of the grain boundaries of the ceria can be extrinsically modified. The introduction of a small amount (< 0.5 mol%) of transition metals (Fe, Co, Mn and Cu) to 1 mol% Gd-doped ceria results in significant reductions in only the grain boundary resistivities of the samples attributed to exclusive segregation of the transition metals into the grain boundary core. In the case of Co- and Fe-doped samples, the grain boundary resistivity is lowered by an order of magnitude. EELS line scans across the grain boundaries of the Fe-doped sample have indicated that the grain boundaries are free of a secondary phase of transition metal oxide and that the Fe in the grain boundary likely exists as point defects. These results strongly suggest that it is indeed possible to reduce the excess positive charge in the grain boundary core, and thus the grain boundary resistivity in a ceria electrolyte, extrinsically as initially postulated. A defect chemistry model which explains partial counterbalance to the positive grain boundary core charge has been suggested. The resistivity minimum shown for the samples with different Fe concentration indicates that there is an optimum concentration of transition metal in the grain boundary core of the ceria necessary for such a countbalance.     

Grain Boundary Kinetics in Oxide Ceramics with the Cubic Fluorite Crystal Structure and its Derivatives

Kinetics of grain boundaries in oxides with the cubic fluorite structure and its derivatives has been investigated using fine grain ceramics that are fully dense. Grain growth measurements in these materials have provided information on grain boundary diffusivity over a diffusion distance of the order of the initial grain size. With the addition of solute cations, grain boundary mobility can be varied over many orders of magnitude, often with very different activation energies. This is caused by the variation of defect population and the defect-solute association. Definitive evidence for solute drag has also been observed in some cases, but solute drag can not be confirmed as a general mechanism in solid solutions. Lastly, while grain boundary at low temperature may continue to serve as a fast diffusion path, it may not be able to migrate because of additional pinning mechanisms such as those exerted by grain boundary nodal points or lines. This means that sintering without grain growth is possible, opening up an avenue for obtaining ultrafine ceramics by pressureless sintering.     

Modification of Electrical Activity of Grain Boundaries in EFG Silicon Under Influence of Hydrogen Plasma

We investigated an influence of hydrogen plasma treatment on electrical properties of shaped silicon polycrystals. Hydrogen penetration into polycrystalline silicon is demonstrated to depend on the state of the crystal (as-grown or annealed) and type of grain boundary (general or weakly deviated from special orientations). It is found that interaction of atomic hydrogen with grain boundaries can result not only in decrease of their electrical activity, but also in increase of potential barrier height at relatively high (more than 2 × 10¹⁸ cm^–2) doses of incorporated hydrogen. This phenomenon is explained by a phenomenological model which takes into account passivation of grain boundary dangling bonds and boron atoms in the bulk as two main mechanisms controlling hydrogenation effect.     

Effects of Surface Anisotropy on Grain Boundary Grooving

The topography of grain boundary thermal grooves in Ni-rich NiAl is studied by atomic force microscopy. It is demonstrated that in many cases the shape of the grooves is remarkably different from the classical shape predicted by Mullins' theory. The presence of singular facets exhibiting no measurable curvature in the region of a grain boundary groove strongly changes the overall morphology of the groove. A quantitative theory of grain boundary grooving, which takes into account surface anisotropy, is developed. Energetic selection criteria for the different groove morphologies are suggested. The calculated and experimentally observed groove morphologies are in a good qualitative agreement.     

Interaction of Solute Impurity with Grain Boundary: The Impurity Drag Effect

An equation of grain boundary motion in a binary polycrystal is derived. The derivation is based on minimization of free energy of the total systems. The equation takes into account an impurity segregation at the grain boundary, grain boundary curvature and energy.As an example, we apply this equation to the analysis of the impurity drag effect problem. It is shown, that the sign of the impurity effect on grain boundary velocity (delay or acceleration) does not depend on kinetic coefficients. The sign of the effect is determined by a thermodynamic function which combines the grain boundary segregation coefficient, the derivative of grain boundary energy with respect to absorbed impurity concentration, and the derivative of bulk free energy with respect to bulk impurity concentration.     

Examination of Dislocation Mechanism on Grain Boundary Sliding in High Angle Grain Boundaries by Stress Change Test

In order to understand the factors dominating grain boundary sliding, stress change tests and stress reversal tests were conducted on aluminum bicrystal specimens with high angle grain boundaries. It is found that small change in stress results in the remarkable change in the rate of grain boundary sliding. Stress reversal tests showed that grain boundary slide hardening does not work for the sliding to the direction opposite to that before the stress reversal. Mean internal stresses for the dislocations contributing to grain boundary sliding are experimentally measured by a method consisting of stress change and annealing. It is found that the velocity of dislocations in the grain boundary is in proportion to the mean effective stress.     

Grain Boundary Dynamics: A Novel Tool for Microstructure Control

The reaction of grain boundaries to a wide spectrum of forces is reviewed. Curvature, volume energy and mechanical forces are considered. The boundary mobility is strongly dependent on misorientation, which is attributed to both grain boundary structure and segregation. In magnetically anisotropic materials grain boundaries can be moved by magnetic forces. For the first time a directionality of boundary mobility is reported. Flat boundaries can also be moved by mechanical forces, which sheds new light on microstructure evolution during elevated temperature deformation. Curvature driven and mechanically moved boundaries can behave differently. A sharp transition between the small and large angle boundary regime is observed. It is shown that grain boundary triple junctions have a finite mobility and thus, may have a serious impact on grain growth in fine grained materials. The various dependencies can be utilized to influence grain boundary motion and thus, microstructure evolution during recrystallization and grain growth.     

Grain boundary compositions in stoichiometric and off-stoichiometric Y1Ba2Cu3O7−x

The grain boundary segregation behavior of stoichiometric and off-stoichiometric YBa₂Cu₃O_7−x has been studied with analytical electron microscopy (AEM) to complement previous results obtained with Auger electron spectroscopy (AES). It was observed that the grain boundary segregation levels varied from boundary to boundary. In stoichiometry material, excess copper and deficient oxygen were observed at the grain boundaries. In materials containing excess barium, excess yttrium and deficient copper levels were observed at the grain boundaries. The grain boundary segregation levels in the materials containing excess barium can be related to the resistivity and critical current density results. Preferential segregation to specific sites in grain boundaries was observed by AEM. The effect of grain boundary segregation on the superconducting properties of these materials is discussed in terms of the weak link behavior and a possible percolative mechanism in order to maintain a continuous current path.     

Grain Boundary Migration in Metals: Recent Developments

Current research on grain boundary migration in metals is reviewed. For individual grain boundaries the dependence of grain boundary migration on misorientation and impurity content are addressed. Impurity drag theory, extended to include the interaction of adsorbed impurities in the boundary, reasonably accounts quantitatively for the observed concentration dependence of grain boundary mobility. For the first time an experimental study of triple junction motion is presented. The kinetics are quantitatively discussed in terms of a triple junction mobility. Their impact on the kinetics of microstructure evolution during grain growth is outlined.     

A new model for electromigration grain boundary noise based on free volume

Grain boundary plays a key role in electromigration process of polycrystal interconnection. We take a free volume to represent a 'vacancy--ion complex' as a function of grain boundary specific resistivity, and develop a new characterisation model for grain boundary noise. This model reveals the internal relation between the boundary scattering section and electromigration noise. Comparing the simulation result with our experimental result, we find the source as well as the form of noise change in the electromigration process. In order to describe the noise enhancement at grain boundary quantitatively, we propose a new parameter-grain boundary noise enhancement factor, which reflects that the grain boundary noise can characterise the electromigration damage sensitively.     

Dynamics of Faceted Grain Boundary Grooves

The dynamics of dislocation-free crystal facets is examined in the context of grain boundary grooves at the junction between two crystallites of a solid and the liquid phase. The geometry and thermal conditions of grain boundary grooves allow a detailed analysis of facet morphology during solidification in terms of the nucleation and spreading rates of elementary crystal planes. Observations on the freezing of water in a two-dimensional cell reveal several dynamical features which are treated by the theory. Additional observations provide indications for the stiffness and premelting of grain boundaries.     

Kinetics of Grain Boundary Recovery in Deformed Polycrystals

Annealing kinetics are studied for nonequilibrium ensembles of dislocations occurring in grain boundaries during plastic deformation. Two types of dislocation ensembles are considered: 1) walls of sessile extrinsic grain boundary dislocations (EGBDs), which cause a change of the GB misorientation angle, and 2) arrays of glissile EGBDs having a Burgers vector tangential to the grain boundary plane. For both types similar exponential relationships are obtained for the relaxation of the average EGBD density, with approximately the same characteristic time proportional to the cube of grain size.     

Significant decrease in interfacial energy of grain boundary through serrated grain boundary transition

The mechanism of serrated grain boundary formation and its effect on liquation behaviour have been studied in a wrought nickel-based superalloy – Alloy 263. It was newly discovered that grain boundaries are considerably serrated in the absence of γ?′-phase or M₂₃C₆ at the grain boundaries. An electron energy-loss spectroscopy study suggests that serration is triggered by the discontinuous segregation of C and Cr atoms at grain boundaries for the purpose of relieving the excessive elastic strain energy. The grain boundaries serrate to have specific segments approaching one {111} low-index plane at a boundary so that the interfacial free energy of the grain boundary can be decreased, which may be responsible for the driving force of the serration. The serrated grain boundaries effectively suppress grain coarsening and are highly resistant to liquation due to their lower wettability resulting from a lower interfacial energy of the grain boundary.     

合金元素韧化或脆化FeAl金属间化合物的微观机制

通过测量二元FeAl以及含B，Zr或Si的FeAl合金的正电子寿命谱参数，计算合金基体和缺陷处的价电子密度.结果表明，当Al原子和Fe原子结合形成FeAl合金时，Al原子提供价电子与Fe原子的3d电子形成局域的共价键.FeAl合金基体的价电子密度很低，FeAl合金中金属键和共价键共存.FeAl合金晶界缺陷的开空间大于Fe空位或Al空位的开空间，FeAl合金晶界处的金属键合力很弱.在FeAl合金中加入少量的B，一部分B原子以间隙方式固溶到FeAl基体中，增加基体的价电子密度；另一部分B原子偏聚到FeAl合金的晶界上，也增加了晶界处的价电子密度.在FeAl合金中加入Zr，增加了合金中的金属键成分，使基体中的价电子密度增加，增强了基体中金属键合力.Zr原子的加入还降低了FeAl合金的有序度，使合金晶界容易弛豫，晶界缺陷的开空间变小.Zr原子在晶界附近出现，还增加了晶界处的价电子密度.在FeAl中加入B或Zr有利于提高合金的韧性.在FeAl合金中加入Si，晶界处的Si原子与邻近的原子形成强的共价键，使得在晶界处参与形成金属键的价电子密度降低.在FeAl中加入Si使合金更脆. 关键词：     

Grain-boundary anelastic relaxation and non-equilibrium dilution induced by compressive stress and its kinetic simulation

Grain boundaries are known to be sources and sinks for bulk vacancies, but the exchange that occurs between the grain boundary and the bulk under a low stress is still obscure. In the present paper, it is shown that grain boundaries may act as sources to emit vacancies when an anelastic deformation occurs under a compressive stress. These emitted supersaturated vacancies are combined with solute atoms to form complexes. Solute non-equilibrium grain-boundary dilution may be induced by the diffusion of complexes away from the boundary. An equation of solute concentration at grain boundary is derived under stress equilibrium during its anelastic relaxation. Furthermore, kinetic equations are also established to describe the non-equilibrium grain-boundary dilution. Additionally, an attempt is made to simulate experimental data to justify the present model.     

Generation of Electrical Currents and Magnetic Fields by Grain Boundary Motion

The effect of an induced magnetic moment due to grain boundary motion in a magnetic field was studied theoretically in a microscopic and a mesoscopic approximation. It was found that the induced moment generates a drag force on the boundary, which depends on the orientation of the magnetic field with regard to the crystal axis, as observed experimentally. However, the magnitude of the theoretically predicted dependency is much smaller than experimentally observed and even opposite with regard to the orientation dependence. Therefore, the electromagnetic drag can be neglected in comparison with other driving forces for grain boundary motion, but the effect may play a role for fast moving dislocations in a magnetic field.