Glassy dielectric response in Tb2NiMnO6 double perovskite with similarities to a Griffiths phase

Results of frequency-dependent and temperature-dependent dielectric measurements performed on the double-perovskite Tb2NiMnO6 are presented. The real (epsilon(1)(f,T)) and imaginary (epsilon(2)(f,T)) parts of dielectric permittivity show three plateaus suggesting dielectric relaxation originating from the bulk, grain boundaries and the sample-electrode interfaces, respectively. The epsilon(1)(f,T) and epsilon(2)(f,T) are successfully simulated by a RC circuit model. The complex plane of impedance, Z'-Z `', is simulated using a series network with a resistor R and a constant phase element. Through the analysis of epsilon(f,T) using the modified Debye model, two different relaxation time regimes separated by a characteristic temperature, T*, are identified. The temperature variation of R and C corresponding to the bulk and the parameter alpha from modified Debye fit lend support to this hypothesis. Interestingly, the T* compares with the Griffiths temperature for this compound observed in magnetic measurements. Though these results cannot be interpreted as magnetoelectric coupling, the relationship between lattice and magnetism is markedly clear. We assume that the observed features have their origin in the polar nanoregions which originate from the inherent cationic defect structure of double perovskites. Copyright (C) EPLA, 2013

Titanium nitride thin film anode: chemical and microstructural evaluation during electrochemical studies

TIN thin films with (200) fibre texture are deposited on Cu substrate at room temperature using reactive magnetron sputtering. They exhibit a discharge capacity of 172 mu Ah cm(-2) mu m(-1) (300 mAh g(-1)) in a non-aqueous electrolyte containing a Li salt. There is a graded decrease in discharge capacity when cycled between 0.01 and 3.0 V. Electron microscopy investigations indicate significant changes in surface morphology of the cycled TiN electrodes in comparison with the as deposited TiN films. From XPS depth profile analysis, it is inferred that Li intercalated TIN films consist of lithium compounds, hydroxyl groups, titanium sub oxides and TiN. Lithium diffusivity and reactivity decrease with increase in depth and the major reaction with lithium takes place at film surface and grain boundaries. (C) 2014 Elsevier Ltd. All rights reserved.

Creep in nanocrystalline zirconia

Grain boundary sliding remains a dominant deformation process during creep in both nanocrystalline and submicron-grained zirconia. The level of segregation of Y to grain boundaries is reduced by a factor of similar to 2 in nanocrystals. However, a scaling relationship for compression creep was valid in a 3 mol.% yttria-stabilized tetragonal zirconia with grain sizes in the range of similar to 65-400 nm, indicating the same deformation mechanism over this range of grain sizes. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Microstructure Development, Nanomechanical, and Dynamic Compression Properties of Spark Plasma Sintered TiB2-Ti-Based Homogeneous and Bi-layered Composites

The growing threats due to increased use of small-caliber armor piercing projectiles demand the development of new light-weight body armor materials. In this context, TiB2 appears to be a promising ceramic material. However, poor sinterability and low fracture toughness remain two major issues for TiB2. In order to address these issues together, Ti as a sinter-aid is used to develop TiB2-(x wt pct Ti), (x = 10, 20) homogeneous composites and a bi-layered composite (BLC) with each layer having Ti content of 10 and 20 wt pct. The present study uniquely demonstrates the efficacy of two-stage spark plasma sintering route to develop dense TiB2-Ti composites with an excellent combination of nanoscale hardness (similar to 36 GPa) and indentation fracture toughness (similar to 12 MPa m(1/2)). In case of BLC, these properties are not compromised w.r.t. homogeneous composites, suggesting the retention of baseline material properties even in the bi-layer design due to optimal relief of residual stresses. The better indentation toughness of TiB2-(10 wt pct Ti) and TiB2-(20 wt pct Ti) composites can be attributed to the observed crack deflection/arrest, indicating better damage tolerance. Transmission electron microscope investigation reveals the presence of dense dislocation networks and deformation twins in alpha-Ti at the grain boundaries and triple pockets, surrounded by TiB2 grains. The dynamic strength of around 4 GPa has been measured using Split Hopkinson Pressure Bar tests in a reproducible manner at strain rates of the order of 600 s(-1). The damage progression under high strain rate has been investigated by acquiring real time images for the entire test duration using ultra-high speed imaging. An attempt has been made to establish microstructure-property correlation and a simple analysis based on Mohr-Coulomb theory is used to rationalize the measured strength properties.

Role of Cu2+ ions substitution in magnetic and conductivity behavior of nano-CoFe2O4

Cobalt copper ferrite nanopowders with composition Co1-xCu5Fe2O4 (0.0 <= x <= 0.5) was synthesized by solution combustion method. The powder X-ray diffraction studies reveal the formation of single ferrite phase with particle size of similar to 11-35 nm. Due to increase in electron density with in a material, X-ray density increase with increase of Cu2+ ions concentration. As Cu2+ ions concentration increases, saturation magnetization decreases from 38.5 to 26.7 emu g(-1). Further, the squareness ratio was found to be similar to 0.31-0.46 which was well below the typical value 1, which indicates the existence of single domain isolated ferrimagnetic samples. The dielectric and electrical modulus was studied over a frequency range of 1 Hz to 1 MHz at room temperature using the complex impedance spectroscopy technique. Impedance plots showed only one semi-circle which corresponds to the contributions of grain boundaries. The lower values of dielectric loss at higher frequency region may be quite useful for high frequency applications such as microwave devices. (C) 2014 Elsevier B.V. All rights reserved.

Diffusion of components via different modes during growth of the A15-V(3)Gaphase

Based on an interdiffusion study using an incremental diffusion couple in the V-Ga binary system, we have shown that V diffuses via the lattice, whereas Ga does so via grain boundaries, for the growth of the V3Ga phase. We estimate the contributions from the two different mechanisms, which are usually difficult to delineate in an interdiffusion study. Available tracer diffusion studies and the atomic arrangement in the crystal structure have been considered for a discussion on the diffusion mechanisms.

Microstructure-hardness-fretting wear resistance correlation in ultrafine grained Cu-TiB2-Pb composites

The retention of the desired combination of mechanical/tribological properties in ultrafine grained materials presents important challenges in the field of bulk metallic composites. In order to address this aspect, the present work demonstrates how one can achieve a good combination of hardness and wear resistance in Cu-Pb-TiB2 composites, consolidated by spark plasma sintering at low temperatures ( < 500 degrees C). Transmission electron microscope (TEM) studies reveal ultrafine grains of Cu (100-400 nm) with coarser TiB2 particles (1-2 mu m) along with fine scale Pb dispersoid at triple junctions or at the grain boundaries of Cu. Importantly, a high hardness of around 2.2 GPa and relative density of close to 90% relative density (rho(theo)) have been achieved for Cu-15 wt% TiB2-10 wt% Pb composite. Such property theo, combination has never been reported for any Cu-based nanocomposite, by conventional processing route. In reference to the tribological performance, fretting wear tests were conducted on the sintered nanocomposites and a good combination of steady state COF (0.6-0.7) and wear rate (10-4 mm(3)/N m) were measured. An inverse relationship between wear rate and hardness was recorded and this commensurates well with Archard's relationship of abrasive wear. The formation of a wear-resistant delaminated tribolayer consisting of TiB2 particles and ultrafine oxide debris, (Cu, Fe, Ti)(x)O-y as confirmed from subsurface imaging using focused ion beam microscopy has been identified as the key factors for the low wear rate of these composites. (C) 2014 Elsevier B.V. All rights reserved.

Domain size correlated magnetic properties and electrical impedance of size dependent nickel ferrite nanoparticles

We report here the investigations on the size dependent variation of magnetic properties of nickel ferrite nanoparticles. Nickel ferrite nanoparticles of different sizes (14 to 22 nm) were prepared by the sol-gel route at different annealing temperatures. They are characterized by TGA-DTA, XRD, SEM, TEM and Raman spectroscopy techniques for the confirmation of the temperature of phase formation, thermal stability, crystallinity, morphology and structural status of the nickel ferrite nanoparticles. The magnetization studies revealed that the saturation magnetization (M-s), retentivity (M-r) increase, while coercivity (H-c) and anisotropy (K-eff) decrease as the particle size increases. The observed value of M-s is found to be relatively higher for a particle size of 22 nm. In addition, we have estimated the magnetic domain size using magnetic data and correlated to the average particle size. The calculated magnetic domain size is closely matching with the particle size estimated from XRD. Impedance spectroscopy was employed to study the samples in an equivalent circuit to understand their transport phenomena. It shows that nickel ferrite nanoparticles exhibit a non-Debye behavior with increasing particle size due to the influence of increasing disorders, surface effects, grain size and grain boundaries, etc. (C) 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

Insights on Defect-Mediated Heterogeneous Nucleation of Graphene on Copper

The grain size of monolayer large area graphene is key to its performance. Microstructural design for the desired grain size requires a fundamental understanding of graphene nucleation and growth. The two levers that can be used to control these aspects are the defect density, whose population can be controlled by annealing, and the gas-phase supersaturation for activation of nucleation at the defect sites. We observe that defects on copper surface, namely dislocations, grain boundaries, triple points, and rolling marks, initiate nucleation of graphene. We show that among these defects dislocations are the most potent nucleation sites, as they get activated at lowest supersaturation. As an illustration, we tailor the defect density and supersaturation to change the domain size of graphene from <1 mu m(2) to >100 mu m(2). Growth data reported in the literature has been summarized on a supersaturation plot, and a regime for defect-dominated growth has been identified. In this growth regime, we demonstrate the spatial control over nucleation at intentionally introduced defects, paving the way for patterned growth of graphene. Our results provide a unified framework for understanding the role of defects in graphene nucleation and can be used as a guideline for controlled growth of graphene.

Magnetic frustration and dielectric relaxation in insulating Nd2NiMnO6 double perovskites

We have investigated structural, dielectric, and magnetic properties of polycrystalline double perovskite Nd2NiMnO6 compound. The compound crystallizes in monoclinic P2(1)/n symmetry and is partially B-site disordered depending on the synthesis conditions. It undergoes second-order ferromagnetic transition at 192K and shows glassy behaviour at low temperature. The glassy phase is due to anti-site disorder within the homogeneous sample. Temperature and frequency dependent dielectric measurements reveal colossal values of dielectric constant and is best interpreted using Maxwell-Wagner interfacial polarization model. Impedance spectroscopy has been used to analyse the intrinsic dielectric response. This enabled us to differentiate the conduction process at the grain and grain boundaries. Arrhenius behaviour is favoured at the grain boundary, while variable range hopping mechanism is considered most suitable within the grain region. dc conductivity measurements corroborate variable range hopping conduction. (C) 2015 AIP Publishing LLC.

Origin of 1/f noise in graphene produced for large-scale applications in electronics

The authors report a detailed investigation of the flicker noise (1/f noise) in graphene films obtained from chemical vapour deposition (CVD) and chemical reduction of graphene oxide. The authors find that in the case of polycrystalline graphene films grown by CVD, the grain boundaries and other structural defects are the dominant source of noise by acting as charged trap centres resulting in huge increase in noise as compared with that of exfoliated graphene. A study of the kinetics of defects in hydrazine-reduced graphene oxide (RGO) films as a function of the extent of reduction showed that for longer hydrazine treatment time strong localised crystal defects are introduced in RGO, whereas the RGO with shorter hydrazine treatment showed the presence of large number of mobile defects leading to higher noise amplitude.

Texture evolution during hot deformation of Moly-TZM

Moly-TZM was deformed at constant strain rate of 1.0 s(-1) to investigate the high strain rate deformation behaviour by microstructural and stress response change within a temperature range of 1400-1700 degrees C. To correlate the deformation behaviour with orientational change, recrystallization and recovery of the material, the microstructural investigation was undertaken using scanning electron microscopy (SEM) of electron back scattered diffraction (EBSD). Depending on the grain size and orientation spread recrystallized grains were identified and texture was calculated. Change in grain boundary characteristics with increasing temperature was determined by the misorientation angle distribution for the deformed and recrystallized grains. Subgrain coalescence and increase in subgrain size with increasing temperature was observed, indicating recrystallization not only occurred from the nucleation of the dislocation free grains in grain boundaries but also from the subgrain rotation and merging of the subgrains by annihilation of the low angle grain boundaries. Detailed studies on the evolution of texture of recrystallized grains showed continuous increase in <001> fiber texture in recrystallised grains, in contrast to a mixed fiber <001> +<111> for the deformed grains.

Review: Overcoming the paradox of strength and ductility in ultrafine-grained materials at low temperatures

Ultrafine-grained (UFG) materials with grain sizes in the submicrometer or nanometer range may be prepared through the application of severe plastic deformation (SPD) to bulk coarse-grained solids. These materials generally exhibit high strength but only very limited ductility in low-temperature testing, thereby giving rise to the so-called paradox of strength and ductility. This paradox is examined and a new quantitative diagram is presented which permits the easy insertion of experimental data. It is shown that relatively simple procedures are available for achieving both high strength and high ductility in UFG materials including processing the material to a very high strain and/or applying a very short-term anneal immediately after the SPD processing. Significant evidence is now available demonstrating the occurrence of grain boundary sliding in these materials at low temperatures, where this is attributed to the presence of non-equilibrium grain boundaries and the occurrence of enhanced diffusion along these boundaries.

Linking monazite geochronology with fluid infiltration and metamorphic histories: Nature and experiment

Migmatised metapelites from the Kodaikanal region, central Madurai Block, southern India have undergone ultrahigh-temperature metamorphism (950-1000 degrees C; 7-8 kbar). In-situ electron microprobe Th-U-Pb isochron (CHIME) dating of monazites in a leucosome and surrounding silica-saturated and silica-poor restites from the same outcrop indicates three principal ages that can be linked to the evolutionary history of these rocks. Monazite grains from the silica-saturated restite have well-defined, inherited cores with thick rims that yield an age of ca. 1684 Ma. This either dates the metamorphism of the original metapelite or is a detrital age of inherited monazite. Monazite grains from the silica-poor restite, thick rims from the silica-saturated restite, and monazite cores from the leucosome have ages ranging from 520 to 540 Ma suggesting a mean age of 530 Ma within the error bars. In the leucosome the altered rim of the monazite gives an age of ca. 502 Ma. Alteration takes the form of Th-depleted lobes of monazite with sharp curvilinear boundaries extending from the monazite grain rim into the core. We have replicated experimentally these altered rims in a monazite-leucosome experiment at 800 degrees C and 2 kbar. This experiment, coupled with earlier published monazite-fluid experiments involving high pH alkali-bearing fluids at high P-T, helps to confirm the idea that alkali-bearing fluids, in the melt and along grain boundaries during crystallization, were responsible for the formation of the altered monazite grain rims via the process of coupled dissolution-reprecipitation. (C) 2015 Elsevier B.V. All rights reserved.

Investigation on the origin of exchange bias in epitaxial, oriented and polycrystalline Fe3O4 thin films

We observe exchange bias (EB) in a single magnetic film Fe3O4 at temperature T < 200 K. Irrespective of crystallographic orientations of grown Fe3O4; they exhibit similar nature of EB for (100) epitaxial, (111) oriented and polycrystalline Fe3O4 thin films. Growth induced defects such as anti-phase boundaries (APBs) in epitaxial Fe3O4 thin film is known to have an influence on the magnetic interaction. But, it is noticed that according to the common consensus of APBs alone cannot explain the origin of EB. If majority of APBs end up with mainly anti-ferromagnetic interactions across these boundaries together with the internal ordering modification in Fe3O4, then EB can emerge at low temperatures. Hence, we propose the idea of directional anti-ferromagnetic APB induced EB in Fe3O4 triggered by internal ordering for T <= 200 K. Similar arguments are extended to (111) oriented as well as polycrystalline Fe3O4 films where the grain boundaries can impart same consequence as that of APBs. (C) 2015 Author(s).