Showing papers on "Grain boundary published in 2002"

CaCu3Ti4O12: One-step internal barrier layer capacitor

Abstract: There has been much recent interest in a so-called “giant-dielectric phenomenon” displayed by an unusual cubic perovskite-type material, CaCu3Ti4O12; however, the origin of the high permittivity has been unclear [M. A. Subramanian, L. Dong, N. Duan, B. A. Reisner, and A. W. Sleight, J. Solid State Chem. 151, 323 (2000); C. C. Homes, T. Vogt, S. M. Shapiro, S. Wakimoto, and A. P. Ramirez, Science 293, 673 (2001); A. P. Ramirez, M. A. Subramanian, M. Gardel, G. Blumberg, D. Li, T. Vogt, and S. M. Shapiro, Solid State Commun. 115, 217 (2000)]. Impedance spectroscopy on CaCu3Ti4O12 ceramics demonstrates that they are electrically heterogeneous and consist of semiconducting grains with insulating grain boundaries. The giant-dielectric phenomenon is therefore attributed to a grain boundary (internal) barrier layer capacitance (IBLC) instead of an intrinsic property associated with the crystal structure. This barrier layer electrical microstructure with effective permittivity values in excess of 10 000 can be fa...

Grain boundaries in high- T c superconductors

Abstract: Since the first days of high-Tc superconductivity, the materials science and the physics of grain boundaries in superconducting compounds have developed into fascinating fields of research. Unique electronic properties, different from those of the grain boundaries in conventional metallic superconductors, have made grain boundaries formed by high-Tc cuprates important tools for basic science. They are moreover a key issue for electronic and large-scale applications of high-Tc superconductivity. The aim of this review is to give a summary of this broad and dynamic field. Starting with an introduction to grain boundaries and a discussion of the techniques established to prepare them individually and in a well-defined manner, the authors present their structure and transport properties. These provide the basis for a survey of the theoretical models developed to describe grain-boundary behavior. Following these discussions, the enormous impact of grain boundaries on fundamental studies is reviewed, as well as high-power and electronic device applications.

Three-dimensional X-ray structural microscopy with submicrometre resolution

Abstract: Advanced materials and processing techniques are based largely on the generation and control of non-homogeneous microstructures, such as precipitates and grain boundaries. X-ray tomography can provide three-dimensional density and chemical distributions of such structures with submicrometre resolution; structural methods exist that give submicrometre resolution in two dimensions; and techniques are available for obtaining grain-centroid positions and grain-average strains in three dimensions. But non-destructive point-to-point three-dimensional structural probes have not hitherto been available for investigations at the critical mesoscopic length scales (tenths to hundreds of micrometres). As a result, investigations of three-dimensional mesoscale phenomena--such as grain growth, deformation, crumpling and strain-gradient effects--rely increasingly on computation and modelling without direct experimental input. Here we describe a three-dimensional X-ray microscopy technique that uses polychromatic synchrotron X-ray microbeams to probe local crystal structure, orientation and strain tensors with submicrometre spatial resolution. We demonstrate the utility of this approach with micrometre-resolution three-dimensional measurements of grain orientations and sizes in polycrystalline aluminium, and with micrometre depth-resolved measurements of elastic strain tensors in cylindrically bent silicon. This technique is applicable to single-crystal, polycrystalline, composite and functionally graded materials.

Grain Boundaries and Dislocations

Abstract: The hardness of coarse-grained materials is inversely proportional to the square root of the grain size. But as Van Swygenhoven explains in her Perspective, at nanometer scale grain sizes this relation no longer holds. Atomistic simulations are providing key insights into the structural and mechanical properties of nanocrystalline metals, shedding light on the distinct mechanism by which these materials deform.

Origin of compressive residual stress in polycrystalline thin films.

Abstract: We present a model for compressive stress generation during thin film growth in which the driving force is an increase in the surface chemical potential caused by the deposition of atoms from the vapor. The increase in surface chemical potential induces atoms to flow into the grain boundary, creating a compressive stress in the film. We develop kinetic equations to describe the stress evolution and dependence on growth parameters. The model is used to explain measurements of relaxation when growth is terminated and the dependence of the steady-state stress on growth rate.

Parameters controlling microstructure and hardness during friction-stir welding of precipitation-hardenable aluminum alloy 6063

Abstract: The aluminum (Al) alloys 6063-T5 and T4 were friction-stir welded at different tool rotation speeds (R), and then distributions of the microstructure and hardness were examined in these welds. The maximum temperature of the welding thermal cycle rose with increasing R values. The recrystallized grain size of the weld increased exponentially with increasing maximum temperature. The relationship between the grain size and the maximum temperature satisfied the static grain-growth equation. In the as-welded condition, 6063-T5 Al was softened around the weld center, whereas 6063-T4 Al showed homogeneous hardness profiles. Different R values did not result in significant differences in the hardness profile in these welds, except for the width of the softened region in the weld of 6063-T5 Al. Postweld aging raised the hardness in most parts of the welds, but the increase in hardness was small in the stir zone produced at the lower R values. Transmission electron microscope (TEM) observations detected a similar distribution of the strengthening precipitates in the grain interiors and the presence of a precipitation-free zone (PFZ) adjacent to the grain boundaries in all the welds. Microstructural analyses suggested that the small increase in hardness in the stir zone produced at the lower R values was caused by an increase in the volume fraction of PFZs.

Atomic mechanism for dislocation emission from nanosized grain boundaries

Abstract: The present work deals with the atomic mechanism responsible for the emission of partial dislocations from grain boundaries (GB's) in nanocrystalline metals. It is shown that in 12 and 20 nm grain size samples GB's containing GB dislocations can emit a partial dislocation during deformation by local atomic shuffling and stress-assisted free volume migration. The free volume is often emitted or absorbed in a neighboring triple junction. It is further suggested that the degree of delocalization surrounding the grain boundary dislocation determines whether atomic shuffling can associate displacements into the Burgers vector necessary to emit a partial dislocation. Temporal analysis of atomic configurations during dislocation emission indicates that creation and propagation of the partial might be separate processes.

Grain-size-sensitive seismic wave attenuation in polycrystalline olivine

Abstract: [1] In order to investigate the processes responsible for the attenuation of seismic shear waves in the Earth's upper mantle, four olivine polycrystals ranging in mean grain size d from 3 to 23 μm have been fabricated, characterized, and mechanically tested in torsion at high temperatures and seismic frequencies. Both the shear modulus, which governs the shear wave speed VS, and the dissipation of shear strain energy Q−1 have been measured as functions of oscillation period To, temperature T, and, for the first time, grain size. At sufficiently high T all four specimens display similar absorption band viscoelastic behavior, adequately represented for 1000 < T < 1200 or 1300°C and 1 < To < 100 s, by the expression Q−1 = A [Tod−1 exp (−E/RT)]α with A = 7.5 × 102 s−α μmα, α = 0.26 and E = 424 kJ mol−1. This mildly grain-size-sensitive viscoelastic behavior of melt-free polycrystalline olivine is attributed to a combination of elastically and diffusionally accommodated grain boundary sliding, the latter becoming progressively more important with increasing T and/or To. Extrapolation to the larger (mm-cm) grain sizes expected in the Earth's upper mantle yields levels of dissipation comparable with those observed seismologically, implying that the same grain-size-sensitive processes might be responsible for much of the observed seismic wave attenuation. The temperature sensitivity of VS is increased substantially by the viscoelastic relaxation allowing the lateral variability of wave speeds to be associated with relatively small temperature perturbations.

Electrical conductivity and dielectric behaviour of nanocrystalline NiFe2O4 spinel

Abstract: Electrical conductivity and dielectric measurements have been performed for nanocrystalline NiFe2O4 spinel for four different average grain sizes, ranging from 8 to 97 nm. The activation energy for the grain and grain boundary conduction and its variation with grain size have been reported in this paper. The conduction mechanism is found to be due to the hopping of both electrons and holes. The high-temperature conductivity shows a change of slope at about 500 K for grain sizes of 8 and 12 nm and this is attributed to the hole hopping in tetrahedral sites of NiFe2O4. Since the activation energy for the dielectric relaxation is found to be almost equal to that of the dc conductivity, the mechanism of electrical conduction must be the same as that of the dielectric polarization. The real part e' of the dielectric constant and the dielectric loss tanδ for the 8 and 12 nm grain size samples are about two orders of magnitude smaller than those of the bulk NiFe2O4. The anomalous frequency dependence of e' has been explained on the basis of hopping of both electrons and holes. The electrical modulus analysis shows the non-Debye nature of the nanocrystalline nickel ferrite.

Twinning, dynamic recovery and recrystallization in hot worked Mg–Al–Zn alloy

Abstract: The AZ31 Mg alloy was hot torsion tested from 180 to 450 °C and from 0.01 to 1.0 s −1 . The flow curves showed a peak and a decline towards a steady-state regime which were lower as temperature T rose and strain rate declined; however, the fracture strain increased to about 1.9 at 0.1 s −1 . In transmission electron microscopy, twins were observed from 180 to 360 °C (in declining numbers). At low T , they had sharp walls and contrasting transverse bands; while the matrix showed indistinct linear streaks. As T rose, the twin bands developed cells with tangled walls and finally subgrains (∼360 °C), while the twin walls became tangles of dislocations and finally serrated boundaries. The matrix developed elongated dislocation walls and subgrains at higher T . The twin intersections at 180 and 240 °C consisted of diamond-shaped cells with a duplex set of orientations but at 300 and 360 °C, these had developed into polygonal cells with high misorientations in dark field. The first very small dynamically recrystallized grains were observed at these intersections, slightly larger than the cells. At 360–450 °C, as observed by optical microscopy, small dynamically recrystallized grains formed at the original grain boundaries, probably related to multiple slip. Since twinning and other features described at low T were also found at high ones, albeit with decreasing frequency, the microstructures showed severe heterogeneity which accounted for the limited ductility.

Physical Origins of Intrinsic Stresses in Volmer–Weber Thin Films

Abstract: As-deposited thin films grown by vapor deposition often exhibit large intrinsic stresses that can lead to film failure. While this is an “old” materials problem, our understanding has only recently begun to evolve in a more sophisticated fashion. Sensitive real-time measurements of stress evolution during thin-film deposition reveal a generic compressive-tensile-compressive behavior that correlates with island nucleation and growth, island coalescence, and postcoalescence film growth. In this article, we review the fundamental mechanisms that can generate stresses during the growth of Volmer-Weber thin films. Compressive stresses in both discontinuous and continuous films are generated by surface-stress effects. Tensile stresses are created during island coalescence and grain growth. Compressive stresses can also result from the flux-driven incorporation of excess atoms within grain boundaries. While significant progress has been made in this field recently, further modeling and experimentation are needed to quantitatively sort out the importance of the different mechanisms to the overall behavior.

Improved superconducting properties in nanocrystalline bulk MgB2

Abstract: High density nanocrystalline MgB2 bulk superconductors with distinctly improved pinning were prepared by mechanical alloying of Mg and B powders at ambient temperatures followed by hot pressing. The nanocrystalline samples reveal high jc=105 A/cm2 at 20 K and 1 T together with an irreversibility line strongly shifted towards higher fields resulting in Hirr(T)∼0.8 Hc2(T), whereas typically Hirr(T)∼0.5 Hc2(T) is observed for untextured bulk samples. These values exceed those of all other reported bulk samples and are in the range of values for thin films. The improved pinning of this material, which mainly consists of spherical grains about 40–100 nm in size, is attributed to the large number of grain boundaries in the nanocrystalline state.

Crystal plasticity model with enhanced hardening by geometrically necessary dislocation accumulation

Abstract: A strain gradient dependent crystal plasticity approach is used to model the constitutive behaviour of polycrystal FCC metals under large plastic deformation. Material points are considered as aggregates of grains, subdivided into several fictitious grain fractions: a single crystal volume element stands for the grain interior whereas grain boundaries are represented by bi-crystal volume elements, each having the crystallographic lattice orientations of its adjacent crystals. A relaxed Taylor-like interaction law is used for the transition from the local to the global scale. It is relaxed with respect to the bi-crystals, providing compatibility and stress equilibrium at their internal interface. During loading, the bi-crystal boundaries deform dissimilar to the associated grain interior. Arising from this heterogeneity, a geometrically necessary dislocation (GND) density can be computed, which is required to restore compatibility of the crystallographic lattice. This effect provides a physically based method to account for the additional hardening as introduced by the GNDs, the magnitude of which is related to the grain size. Hence, a scale-dependent response is obtained, for which the numerical simulations predict a mechanical behaviour corresponding to the Hall–Petch effect. Compared to a full-scale finite element model reported in the literature, the present polycrystalline crystal plasticity model is of equal quality yet much more efficient from a computational point of view for simulating uniaxial tension experiments with various grain sizes.

Microstructure evolution and thermal properties in nanocrystalline Cu during mechanical attrition

Abstract: The microstructural evolution and thermal properties of nanocrystalline (nc) Cu during mechanical attrition were investigated by using quantitative x-ray-diffraction and thermal analysis techniques. Upon milling of the Cu powders with coarse grains, the grain sizes are found to decrease gradually with the milling time, and remain unchanged at a steady-state value (about 11 nm) with continued milling. The microstrain and the stored enthalpy increase to maximum values during the grain refinement, and decrease then increase to the second maxima and decrease again within the milling stage of steady-state grain size, while the lattice parameter remains unchanged during the entire milling process. The grain boundary (GB) enthalpy of the nc Cu was estimated, showing a GB softening-hardening-softening cyclic variation within the steady-state milling. The present work indicated with clear experimental evidence that even within the milling stage of steady-state grain size, the microstructure (both the GB's and the crystallites) of nc materials is still changing, which may result from the GB sliding.

Stress corrosion cracking of sensitized AA5083 (Al-4.5Mg-1.0Mn)

Abstract: The AA5083 (Al-4.4Mg-0.7Mn-0.15Cr) alloy is a nonheat-treatable aluminum alloy known for its excellent corrosion resistance. However, it can become susceptible to intergranular stress corrosion cracking (IGSCC) when exposed to temperatures ranging from 50 °C to 200 °C for sufficient lengths of time. This IGSCC is widely believed to be associated with dissolution of the electrochemically active β phase, Al3Mg2, which is precipitated on grain boundaries. Recently, alternative mechanisms have been invoked related to hydrogen effects and/or free Mg segregation or depletion in the grainboundary regions. To establish a baseline for the sensitization effect, constant-extension-rate tests (CERTs) were conducted under open-circuit conditions and under potential control in 3.5 pct NaCl on samples isothermally treated at 150 °C. To aid in interpreting the CERT results, grain-boundary precipitation and solute depletion were characterized by transmission electron microscopy (TEM). Additionally, the electrochemical behavior of the β phase was characterized by anodic polarization of the intermetallic compound synthesized in bulk form. In CERTs under open-circuit conditions, the measured ductility depended strongly on sensitization time, reaching a minimum at 189 hours, followed by a slight increase at longer times. This trend correlated well with the fractional coverage of β phase on grain boundaries, which increased up to 189 hours, where it existed with nearly continuous coverage. At longer times, this film coarsened and became discontinuous. Correspondingly, some resistance to IGSCC was recovered. In polarization experiments, bulk synthesized β phase was found to be spontaneously passive from its corrosion potential (−1.40 VSCE) up to about −0.92 VSCE, where passivity was observed to break down. Sensitized AA5083 samples polarized below the β-phase breakdown potential showed almost no evidence of IGSCC, indicating that a high β dissolution rate is a requirement for IGSCC. Mg-depleted zones were observed along grain boundaries in sensitized alloys, but a clear role for solute depletion in IGSCC could not be defined on the basis of the results developed in this study.

Segregation effects at grain boundaries in fluorite-structured ceramics

Abstract: The atomic-scale structure, composition, and chemistry of grain boundaries in two fluorite-structured ceramic materials were characterized by a combination of Z-contrast imaging and electron energy-loss spectroscopy (EELS). In the case of a symmetric 24° [001] tilt bicrystal of yttria-stabilized-zirconia (YSZ), a shift in the zirconium M-edge onset and a change in the yttrium and zirconium M-edge ratios at the boundary indicate an increase in the number of electrons in the boundary plane. A detailed study of the structure and composition indicates that this is caused by an increase in the number of oxygen vacancies in the grain boundary core that is partially compensated by yttrium segregation. Studies of grain boundaries in an industrial Gd-doped ceria ceramic reveals similar changes in vacancy/dopant profiles indicating that these effects may be generic to grain boundaries in fluorite-structured materials.