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.     

Low frequency electroluminescence in ferroelectric BaTiO3 single crystals

Electroluminescence has been studied in ferroelectric BaTiO₃ single crystals. The variation of EL with potential temperature and d.c. biasing suggests the existence of complex surface charge layer on the surface of these crystals. The mode of growth of EL pulses reveals the nature of these layers.     

The Elimination of Grains and Grain Boundaries in Grain Growth

The topological changes that occur during coarsening of 2D and 3Dcellular structures, such as polycrystals, areinvestigated. Particular attention is given to the elimination ofgrain boundaries and grains with more than the minimum number oftopological elements. A thermodynamic criterion is introduced tofind out which topological transformations are favoured, based on theevaluation of the Gibbs free energy of the initial and finalconfigurations. In general, elimination of grains is possible only ifthe number of their neighbours is below a critical value, which maybe affected by geometry.     

X-ray and dielectric characterization of Co doped tetragonal BaTiO3 ceramics

ABSTRACT

The crystal structure modifications of BaTiO₃ induced by cobalt doping were studied. The polycrystalline (1 ? x)BaTiO₃ + xCo₂O₃ samples, with x ≤ 10 wt.%, were prepared by high temperature sintering conventional method. According to X-ray phase and structural characterization, performed by full-profile Rietveld refinement technique, all synthesized samples showed tetragonal symmetry perovskite structure with minor amount of parasitic phases. Pure single-phase composition has been detected only in the low level of doping BaTiO₃. It was indicated that substitution of Co for the Ti sites in the (1 ? x)BaTiO₃ + xCo₂O₃ series led to decrease of tetragonality (c/a) of the BaTiO₃ perovskite structure. This effect almost vanished in the (1 ? x)BaTiO₃ + xCo₂O₃ samples with nominal Co content higher than ～1 wt.%, in which precipitation of parasitic Co-containing phases CoO and Co₂TiO₄ has been observed. Based on the results, the solubility limit of Co in Ti sub-lattice in the (1 ? x)BaTiO₃ + xCo₂O₃ series is estimated as x = 0.75 wt.%.     

Microstructure Observations for Diffusion Induced Recrystallization and Diffusion Induced Grain Boundary Migration on Surfaces of Zincified Cu Bicrystals With [1 1 0] Twist Boundaries

The formation behavior of the fine-grain region alloyed with Zn due to diffusion induced recrystallization (DIR) in the Cu(Zn) system was experimentally examined for the surfaces polished in different manners using a Cu bicrystal containing a [1 1 0] twist boundary with a misorientation angle of = 46° zincified at 673 K for 2.88 × 10⁴ s with Cu-15 wt% Zn and Cu-30 wt% Zn alloys by a capsule zincification technique. The extent and morphology of the fine-grain DIR region vary depending on the surface conditions and the composition of the Zn-source Cu-Zn alloy. For the specimen with the surface electrolytically polished in an etchant consisting of 20 vol% of nitric acid and 80 vol% of methanol, no DIR region was formed on the whole surface when the Cu-15 wt% Zn alloy was used as a Zn source.In order to observe the morphology of the moving grain boundary owing to diffusion induced grain boundary migration (DIGM) without influences of DIR, Cu bicrystals with [1 1 0] twist boundaries of = 32 ( 27), 39 ( 9), 46, 51 ( 11) and 55° were electrolytically polished in the etchant mentioned above. The polished Cu bicrystals were zincified at 673 K for 2.88 × 10⁴ s using the Cu-15 wt% Zn alloy as a Zn source. Remarkable surface relief and clear slip bands were recognized on the surfaces due to DIGM for the specimens with the 32 ( 27) and 46° boundaries. The moving boundary became zigzag owing to the slip bands parallel to the moving direction. On the other hand, such surface relief and slip bands were not observed for the specimens with the 39 ( 9), 51 ( 11) and 55° boundaries. The moving boundary was considerably irregular for = 39° whereas rather smooth for = 51 ( 11) and 55°. The migration behavior of the grain boundary was not affected by the interruption of the zincification.     

Effect of Grain Boundary Segregation and Migration on Diffusion Profiles: Analysis and Experiments

In many experimental studies, curved penetration profiles are observed for grain boundary diffusion performed in the B kinetics regime in contrast to the shape expected from the solutions of the second Fick's equation. To explain these curvatures the effects of grain boundary structure, grain boundary migration, and grain boundary segregation have been successively proposed in the literature. Using previous data for Cu–Ag and Cu–Ni and new ones on Cu–Fe and Cu–Zn systems we will show how it is possible to separate all these possible contributions and how, knowing the true origin of the curvature, one can deduce much quantitative information impossible (or very difficult) to obtain by other techniques.     

Size Tunable Synthesis of Highly Crystalline BaTiO3 Nanoparticles using Salt-Assisted Spray Pyrolysis

Highly crystalline, dense BaTiO₃ nanoparticles in a size range from 30 to 360nm with a narrow size distribution (_g = 1.2–1.4) were prepared at various synthesis temperatures using a salt-assisted spray pyrolysis (SASP) method without the need for post-annealing. The effect of synthesis temperature on particle size, crystallinity and surface morphology of the nanoparticles were characterized by X-ray diffraction and scanning/transmission electron microscopy. The nature of the crystalline structure was analyzed by Rietveld refinement and Raman spectroscopy. The particle size decreased with decreasing operation temperature. The crystal phase was transformed from tetragonal to cubic at a particles size of about 50nm at room temperature. SASP can be used to produce high weight fraction of tetragonal BaTiO₃ nanoparticles down to 64nm in a single step.     

Effect of High-Temperature Structure and Diffusion on Grain-Boundary Diffusion Creep in fcc Metals

Molecular dynamics simulations of high-energy twist and tilt bicrystals of fcc palladium reveal a universal, liquid-like, isotropic high-temperature diffusion mechanism, characterized by a rather low self-diffusion activation energy that is independent of the boundary type or misorientation. Medium-energy grain boundaries exhibit the same behavior at the highest temperatures; however, at lower temperatures the diffusion mechanism becomes anisotropic, with a higher, misorientation-dependent activation energy. Our simulations demonstrate that the lower activation energy at elevated temperatures is caused by a structural transition, from a solid boundary structure at low temperatures to a liquid-like structure at high temperatures. We demonstrate that the existence of such a transition has important consequences for diffusion creep in nanocrystalline fcc metals. In particular, our simulations reveal that in the absence of grain growth, nanocrystalline microstructures containing only high-energy grain boundaries exhibit steady-state diffusion creep with a creep rate that agrees quantitatively with that given by the Coble-creep formula. Remarkably, the activation energy for the high-temperature creep rate is the same as that characterizing the universal high-temperature diffusion in high-energy energy bicrystalline grain boundaries.     

Coarsening in Sintering: Grain Shape Distribution,Grain Size Distribution,and Grain Growth Kinetics in Solid-Pore Systems

Sintering occurs when packed particles are heated to a temperature where there is sufficient atomic motion to grow bonds between the particles. The conditions that induce sintering depend on the material, its melting temperature, particle size, and a host of processing variables. It is common for sintering to produce a dimensional change, typically shrinkage, where the powder compact densifies, leading to significant strengthening. Microstructure coarsening is inherent to sintering, most evident as grain growth, but it is common for pore growth to occur as density increases. During coarsening, the grain structure converges to a self-similar character seen in both the grain shape distribution and grain size distribution. Coarsening behavior during sintering conforms to classic grain growth kinetics, modified to reflect the evolving microstructure. These modifications involve the grain boundary coverage due to pores, liquid films, or second phases and the altered grain boundary mobility due to these phases. The mass transport rates associated with each of these interfaces are different, with different temperature and composition dependencies. Hence, the coarsening rate during sintering is not constant, but changes with the evolving microstructure. Core aspects treated in this review include models for coarsening, grain shape, grain size distribution, and how pores, liquids, dispersoids, and other phases determine microstructure coarsening during sintering.     

Grain Boundary Resistivity and Electrically Induced Grain Boundary Migration (EIGM) in Metallic Bamboo Microstructures

As VLSI conductor line dimensions continue to decrease, electrotransport properties increasingly effect device lifetimes. Grain boundaries are intimately linked to these processes, providing paths of varying diffusivity, and as mobile defects themselves. Haessner et al. [6] make a challenging finding in experiments with thin gold films: based on calorimetric data, in order to account for the velocity of grain boundaries migrating in high electric current densities, the force on the atoms of a grain boundary would have to be two orders of magnitude larger than what the accepted theory for bulk ions predicts. The failure is attributed to the simplicity of the model which does not account for possible variations of the resistivity and effective valance charge that could occur in the vicinity of a grain boundary. In this paper, expressions are developed for the electron wind force on the atoms near grain boundaries, and they are written in terms of thermodynamic variables: the boundary specific volume expansion and specific resistivity. The enhancement of the wind force of the boundary atoms over the bulk wind force is calculated using published data. This model allows for more than an order of magnitude enhancement in gold, and Haessner's observation is rationalized.     

Abnormal Raman spectra in Er‐doped BaTiO3 ceramics

Greatly enhanced and abnormal Raman spectra were discovered in the nominal (Ba_{1 − x}Er_x)Ti_{1 − x/4}O₃ (x = 0.01) (BET) ceramic for the first time and investigated in relation to the site occupations of Er³⁺ ions. BaTiO₃ doped with Ti‐site Er³⁺ mainly exhibited the common Raman phonon modes of the tetragonal BaTiO₃. Er³⁺ ions substituted for Ba sites are responsible for the abnormal Raman spectra, but the formation of defect complexes will decrease spectral intensity. A large increase in intensity showed a hundredfold selectivity for Ba‐site Er³⁺ ions over Ti‐site Er³⁺ ions. A strong EPR signal at g = 1.974 associated with ionized Ba vacancy defects appeared in BET, and the defect chemistry study indicated that the real formula of BET is expressed by (Ba_{1 − x}Er_3x/4)(Ti_{1 − x/4}Er_x/4)O₃. These abnormal Raman signals were verified to originate from a fluorescent effect corresponding to ⁴S_3/2→⁴I_15/2 transition of Ba‐site Er³⁺ ions. The fluorescent signals were so intense that they overwhelmed the traditional Raman spectra of BaTiO₃. The significance is that the abnormal Raman spectra may act as a probe for the Ba‐site Er³⁺ occupation in BaTiO₃ co‐doped with Er³⁺ and other dopants. A new broad EPR signal at g = 2.23 was discovered, which originated from Er³⁺ Kramers ions. Copyright © 2014 John Wiley & Sons, Ltd.     

Boundary Mobility and Energy Anisotropy Effects on Microstructural Evolution During Grain Growth

We have performed mesoscopic simulations of microstructural evolution during curvature driven grain growth in two-dimensions using anisotropic grain boundary properties obtained from atomistic simulations. Molecular dynamics simulations were employed to determine the energies and mobilities of grain boundaries as a function of boundary misorientation. The mesoscopic simulations were performed both with the Monte Carlo Potts model and the phase field model. The Monte Carlo Potts model and phase field model simulation predictions are in excellent agreement. While the atomistic simulations demonstrate strong anisotropies in both the boundary energy and mobility, both types of microstructural evolution simulations demonstrate that anisotropy in boundary mobility plays little role in the stochastic evolution of the microstructure (other than perhaps setting the overall rate of the evolution. On the other hand, anisotropy in the grain boundary energy strongly modifies both the topology of the polycrystalline microstructure the kinetic law that describes the temporal evolution of the mean grain size. The underlying reasons behind the strongly differing effects of the two types of anisotropy considered here can be understood based largely on geometric and topological arguments.     

Strain Induced Grain Boundary Premelting along Twin Boundaries in Copper Polycrystals

A polycrystalline copper sample was compressed at room temperature, then the temperature was raised to 873 K in a vacuum and annealed without unloading. Grain boundary cracks were found at 3 coherent twin boundaries. The formation of these cracks can be interpreted based on the idea of strain induced grain boundary premelting (SIGBPM). It is emphasized that 3 twin boundaries can be one of the most dangerous boundaries for crack formation when certain experimental conditions are satisfied.     

Grain Boundary Motion during Ag and Cu Grain Boundary Diffusion in Cu Polycrystals

Grain boundary (GB) motion in high-purity Cu material (5N8 and 5N Cu) is investigated using the results of radiotracer GB diffusion measurements with tracers exhibiting fundamental differences in the solute-matrix atom interactions. The results on GB solute diffusion of Ag (revealing a miscibility gap in the Ag-Cu phase diagram) and Au (forming intermetallic compounds with Cu) in Cu and on Cu self-diffusion are analyzed.The initial parts of the Ag and Cu penetration profiles turned out to be substantially curved. The profile curvature is explained via the effect of GB motion during ^110m Ag and ⁶⁴Cu GB penetration. The activation enthalpies of GB motion in these two independent measurements occurred to be very close, 95 and 103 kJ/mol, respectively. Moreover, these values turn out to be close, but still somewhat larger than the activation enthalpy of Cu GB self-diffusion in Cu material of the same very high purity, Q ^Cu _gb = 72 kJ/mol. Although tracer diffusion measurements of Au GB diffusion in Cu yielded only limited information on GB motion, the absolute values of GB velocities are consistent with those calculated from the Ag and Cu GB diffusion data.     

Normal and Abnormal Grain Growth as Transient Phenomena

For the case of uniform grain boundaries the basic equations of the statistical theory of grain growth (GG) of the present authors are shortly reviewed and compared to the classical Hillert model. On the basis of this present theory normal and abnormal 3-D GG is simulated and particularly the effect of the initial grain size distribution function (SDF) on the GG behaviour which may lead to normal or abnormal GG is demonstrated. Finally results of simulations of normal 2-D GG by the statistical method and by a direct model (curvature driven grain boundaries (GBs)) are presented which exhibit good agreement with one another. It is shown by this comparison that the possibility of finding by such direct methods a self similar SDF as long time asymptote can be excluded because, in contrast to the simulations based on the statistical theory, for the direct models the very large computational capacities required for the long simulation times are not available yet. The conclusion repeatedly claimed in literature that the true self similar SDF deviates from the Hillert distribution can thus be shown not to be justified.     

Triple Junctions Effect on the Grain Growth in Nanostructured Materials

Microstructure evolution and grain growth in nanostructured aluminium films has been examined. The films were produced by vacuum evaporation on NaCl (100) substrate. Time dependences of mean grain area are presented. It has been revealed that the normal grain growth takes place in the films. The obtained data on the normal grain growth in 3-D films were compared with those for 2-D aluminium strips and foils. It was concluded that in the temperature range studied the grain growth kinetics is determined by triple junctions dragging force.     

Self-Pumped Phase Conjugation in a Ce:BaTiO3 Crystal Pumped with Femtosecond Laser Pulses at 1053 nm Wavelength

Self-pumped phase conjugation in a cerium-doped barium titanate crystal pumped with femtosecond laser pulses at a 1053 nm wavelength was experimentally studied. A reflectivity of a self-pumped phase conjugation as high as 15#x0025; was demonstrated.