Lowering grain boundary resistance of BaZr0.8Y0.2O3−δ with LiNO3 sintering-aid improves proton conductivity for fuel cell operation

A novel sintering additive based on LiNO3 was used to overcome the drawbacks of poor sinterability and low grain boundary conductivity in BaZr0.8Y0.2O3-δ (BZY20) protonic conductors. The Li-additive totally evaporated during the sintering process at 1600°C for 6 h, which led to highly dense BZY20 pellets (96.5% of the theoretical value). The proton conductivity values of BZY20 with Li sintering-aid were significantly larger than the values reported for BZY sintered with other metal oxides, due to the fast proton transport in the "clean" grain boundaries and grain interior. The total conductivity of BZY20-Li in wet Ar was 4.45 × 10-3 S cm-1 at 600°C. Based on the improved sinterability, anode-supported fuel cells with 25 μm-thick BZY20-Li electrolyte membranes were fabricated by a co-firing technique. The peak power density obtained at 700°C for a BZY-Ni/BZY20-Li/La0.6Sr0.4Co0.2Fe 0.8O3-δ (LSCF)-BZY cell was 53 mW cm-2, which is significantly larger than the values reported for fuel cells using electrolytes made of BZY sintered with the addition of ZnO and CuO, confirming the advantage of using Li as a sintering aid.

Breakdown in p‐n junction diodes made on polycrystalline silicon of large grain size

This communication describes the voltage‐current characteristics in the breakdown region of p‐n junctions made on polycrystalline silicon of large grain size. The observed soft breakdown characteristics have been explained by taking into account the effect of curvature of the junction near the grain boundaries.

The influence of grain size on deformation of copper

It is well know that grain boundaries enhance strength at low temperatures by acting as obstacles to dislocation motion, and they retard strength at higher temperatures by processes involving grain boundary sliding. The available data on the influence of grain boundaries on deformation in copper is summarized. Equi-channel angular extrusion offers a convenient means for imposing severe plastic deformation to refine the grain size in bulk materials. Experimental data on fine grained copper produced by equi-channel angular extrusion will be described, and the implications of the data for diffusion creep and superplasticity will be discussed.

Grain-Size Effects on the High-Temperature Oxidation of Modified 304 Austenitic Stainless Steel

The high-temperature oxidation behavior of modified 304 austenitic stainless steels in a water vapor atmosphere was investigated. Samples were prepared by various thermo mechanical treatments to result in different grain sizes in the range 8-30 mu m. Similar I 3 pound grain boundary fraction was achieved to eliminate any grain-boundary characteristics effect. Samples were oxidized in an air furnace at 700 A degrees C with 20 % water vapor atmosphere. On the fine-grained sample, a uniform Cr2O3 layer was formed, which increased the overall oxidation resistance. Whereas on the coarse-grained sample, an additional Fe2O3 layer formed on the Cr-rich oxide layer, which resulted in a relatively high oxidation rate. In the fine-grained sample, grain boundaries act as rapid diffusion paths for Cr and provided enough Cr to form Cr2O3 oxide on the entire sample surface.

A Constitutive Equation for Grain Boundary Sliding: An Experimental Approach

Although grain boundary sliding (GBS) has been recognized as an important process during high-temperature deformation in crystalline materials, there is paucity in experimental data for characterizing a constitutive equation for GBS. High-temperature tensile creep experiments were conducted, together with measurements of GBS at different strains, stresses, grain sizes, and temperatures. Experimental data obtained on a Mg AZ31 alloy demonstrate that, for the first time, dynamic recrystallization during creep does not alter the contribution of GBS to creep during high-temperature deformation. The experimentally observed invariance of the sliding contribution with strain was used together with the creep data for developing a constitutive equation for GBS in a manner similar to the standard creep equation. Using this new approach, it is demonstrated that the stress, grain size, and temperature dependence for creep and GBS are identical. This is rationalized by a model based on GBS controlled by dislocations, within grains or near-grain boundaries. (C) The Minerals, Metals & Materials Society and ASM International 2013

Enhancing the high temperature plasticity of a Cu-containing austenitic stainless steel through grain boundary strengthening

The addition of 3 wt% Cu to heat-resistant SUS 304H austenitic steel enhances its high temperature mechanical properties. To further improve the properties, particularly the creep resistance and ductility at high temperatures, a post-solutionizing heat-treatment method that involves an intermediated annealing either at 700 or 800 degrees C after solutionizing for durations up to 180 min was employed. The purpose this heat-treatment is to precipitate planar Cr23C6 at the grain boundaries, which results in the boundaries getting serrated. Detailed microstructural analyses of these `grain boundary engineered' alloys was conducted and their mechanical performance, both at room temperature and at 750 degrees C, was evaluated. While the grain size and texture are unaffected due to the high temperature hold, the volume fraction of Sigma 3 twin boundaries was found to increase significantly. While the strength enhancement was only marginal, the ductility was found to increase significantly, especially at high temperature. A marked increase in the creep resistance was also noted, which is attributed to the reduction of the grain boundary sliding by the grain boundary serrations and the suppression of grain boundary cavitation through the optimization of the volume fraction and spacing of the Cr23C6 precipitates. The special heat-treatment performed with holding time of 3 h at 700 degrees C resulted in the optimum combination of strength, ductility and creep resistance at high temperature. (C) 2014 Elsevier B.V. All rights reserved.

Suppression of grain boundary relaxation in Zr-doped BiFeO3 thin films

Here, we present the results of temperature dependent dielectric studies on chemical solution processed Zr-doped BiFeO3 (BFO) thin films deposited on Pt/Si substrates. We find that in contrast to the undoped BFO films, Zr doping at Fe-site suppresses the low frequency dielectric relaxation originating from the grain boundaries, attributed to the increased dipolar rigidity due to stronger Zr-O bonds. Temperature dependent dc conductivity obtained from impedance and modulus analyses shows two distinct conduction processes occurring inside the grains. At temperature below similar to 423K, conductivity is nearly temperature independent, while in the high temperature regime (above similar to 423K), conduction is governed by the long range movement of oxygen vacancies with an activation energy of similar to 1eV. (C) 2014 AIP Publishing LLC.

Upper Bounds on the Size of Grain-Correcting Codes

In this paper, we revisit the combinatorial error model of Mazumdar et al. that models errors in high-density magnetic recording caused by lack of knowledge of grain boundaries in the recording medium. We present new upper bounds on the cardinality/rate of binary block codes that correct errors within this model. All our bounds, except for one, are obtained using combinatorial arguments based on hypergraph fractional coverings. The exception is a bound derived via an information-theoretic argument. Our bounds significantly improve upon existing bounds from the prior literature.

Exceptional resistance to grain growth in nanocrystalline CoCrFeNi high entropy alloy at high homologous temperatures

Nanocrystalline CoCrFeNi high entropy alloy, synthesized by mechanical alloying followed by spark plasma sintering, demonstrated extremely sluggish grain growth even at very high homologous temperature of 0.68 T-m (900 degrees C) for annealing duration of 600 h. Mechanically alloyed powder had carbon and oxygen as impurities, which in turn led to the formation of two-phase mixture of FCC and Cr-rich carbide with fine distribution of Cr-rich oxide during spark plasma sintering. Sluggish grain growth is attributed to the Zener pinning effect from the fine dispersion of oxide, mutual retardation of grain boundaries in the presence of two phases, and sluggish diffusivity because of cooperative diffusion of multi-principle elements. (C) 2015 Elsevier B.V. All rights reserved.

Grain Refinement at the Nanoscale Via Mechanical Twinning and Dislocation Interaction in a Nickel-Based Alloy

A nanostructured surface layer was formed on an Inconel 600 plate by subjecting it to surface mechanical attrition treatment at room temperature. Transmission electron microscopy and high-resolution transmission electron microscopy of the treated surface layer were carried out to reveal the underlying grain refinement mechanism. Experimental observations showed that the strain-induced nanocrystallization in the current sample occurred via formation of mechanical microtwins and subsequent interaction of the microtwins with dislocations in the surface layer. The development of high-density dislocation arrays inside the twin-matrix lamellae provides precursors for grain boundaries that subdivide the nanometer-thick lamellae into equiaxed, nanometer-sized grains with random orientations.

The Influence of Grain Size and Temperature on the mechanical Deformation of Nanocrystalline Materials: Molecular Dynamics Simulation

Nanocrystalline (nc) materials are characterized by a typical grain size of 1-100nm. The uniaxial tensile deformation of computer-generated nc samples, with several average grain sizes ranging from 5.38 to 1.79nm, is simulated by using molecular dynamics with the Finnis-Sinclair potential. The influence of grain size and temperature on the mechanical deformation is studied in this paper. The simulated nc samples show a reverse Hall-Petch effect. Grain boundary sliding and motion, as well as grain rotation are mainly responsible for the plastic deformation. At low temperatures, partial dislocation activities play a minor role during the deformation. This role begins to occur at the strain of 5%, and is progressively remarkable with increasing average grain size. However, at elevated temperatures no dislocation activity is detected, and the diffusion of grain boundaries may come into play.

Domains beyond the grain boundary

Thin films of inorganic materials are used in diverse applications, typically in polycrystalline form due to their relatively simple production. We have used enhanced piezoresponse force microscopy to investigate the domain distribution within neighbouring grains in thin polycrystalline films of the ferroelectric-ferroelastic system lead zirconate titanate (PZT). We demonstrate that domains are organized into areas with a correlated alignment of the ferroelastic and ferroelectric domains, spanning multiple grain boundaries. We present five typical arrangements of such structures: azimuthal, radial, gradient, and short- and long- range linear domain organizations. Moreover, we discuss the mechanical and electrical constraints that dictate these structures. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Grain Boundary Effects On Plastic Deformation And Fracture Mechanisms In Cu Nanowires: Molecular Dynamics Simulations

Metallic nanowires have many attractive properties such as ultra-high yield strength and large tensile elongation. However, recent experiments show that metallic nanowires often contain grain boundaries, which are expected to significantly affect mechanical properties. By using molecular dynamics simulations, here, we demonstrate that polycrystalline Cu nanowires exhibit tensile deformation behavior distinctly different from their single-crystal counterparts. A significantly lowered yield strength was observed as a result of dislocation emission from grain boundaries rather than from free surfaces, despite of the very high surface to volume ratio. Necking starts from the grain boundary followed by fracture, resulting in reduced tensile ductility. The high stresses found in the grain boundary region clearly play a dominant role in controlling both inelastic deformation and fracture processes in nanoscale objects. These findings have implications for designing stronger and more ductile structures and devices on nanoscale.

Molecular dynamics studies on the dislocation gliding near a tilt boundary

The gliding behavior of edge dislocation near a grain boundary(QB) in copper under pure shear stresses is simulated by using molecular dynamics(MD) method. Many-body potential incorporating the embedded atom method (EAM) is used. The critical shear stresses for a single disocation to pass across GB surface are obtained at values of sigma(c)=23MPa similar to 68 MPa and 137 MPa similar to 274 MPa for Sigma=165 small angle tilt GB at 300 K and 20 K, respectively. The first result agrees with the experimental yield stress sigma(y)(=42 MPa) quite well. It suggests that there might be one of the reasons of initial plastic yielding caused by single dislocation gliding across GB. In addition, there might be possibility to obtain yield strength from microscopic analysis. Moreover, the experimental value of sigma(y) at low temperature is generally higher than that at room temperature. So, these results are in conformity qualitatively with experimental fact. On the other hand, the Sigma=25 GB is too strong an obstacle to the dislocation. In this case, a dislocation is able to pass across GB under relatively low stress only when it is driven by other dislocations. This is taken to mean that dislocation pile-up must be built up in front of this kind of GB, if this GB may take effect on the process of plastic deformation.

Crack growth by grain boundary cavitation in the transient and extensive creep regimes

Crack growth due to cavity growth and coalescence along grain boundaries is analyzed under transient and extensive creep conditions in a compact tension specimen. Account is taken of the finite geometry changes accompanying crack tip blunting. The material is characterized as an elastic-power law creeping solid with an additional contribution to the creep rate arising from a given density of cavitating grain boundary facets. All voids are assumed present from the outset and distributed on a given density of cavitating grain boundary facets. The evolution of the stress fields with crack growth under three load histories is described in some detail for a relatively ductile material. The full-field plane strain finite element calculations show the competing effects of stress relaxation due to constrained creep, diffusion and crack tip blunting. and of stress increase due to the instantaneous elastic response to crack growth. At very high crack growth rates the Hui-Riedel fields dominate the crack tip region. However. the high growth rates are not sustained for any length of time in the compact tension geometry analyzed. The region of dominance of the Hui-Riedel field shrinks rapidly so that the near-tip fields are controlled by the HRR-type field shortly after the onset of crack growth. Crack growth rates under various conditions of loading and spanning the range of times from small scale creep to extensive creep are obtained. We show that there is a strong similarity between crack growth history and the behaviour of the C(t) and C(t) parameters. so that crack growth rates correlate rather well with C(t) and C(t). A relatively brittle material is also considered that has a very different near-tip stress field and crack growth history.