Effect of Manganese (II) Oxide on microstructure and ionic transport properties of nanostructured cubic zirconia

Effect of MnO addition on microstructure and ionic transport properties of nanocrystalline cubic(c)-ZrO2 is reported. Monoclinic (m) ZrO2 powders with 10-30 mol% MnO powder are mechanically alloyed in a planetary ball mill at room temperature for 10 h and annealed at 550 degrees C for 6 h. In all compositions m-ZrO2 transforms completely to nanocrystalline c-ZrO2 phase and MnO is fully incorporated into c-ZrO2 lattice. Rietveld's refinement technique is employed for detailed microstructure analysis by analyzing XRD patterns. High resolution transmission electron microscopy (HRTEM) analysis confirms the complete formation of c-ZrO2 phase. Presence of stoichiometric Mn in c-ZrO2 powder is confirmed by Electron Probe Microscopy analysis. XPS analysis reveals that Mn is mostly in Mn2+ oxidation state. A correlation between lattice parameter and oxygen vacancy is established. A detailed ionic conductivity measurement in the 250 degrees-575 degrees C temperature range describes the effect of MnO on conductivity of c-ZrO2. The ionic conductivity (s) of 30 mol% MnO alloyed ZrO2 at 550 degrees C is 0.04 s cm(-1). Electrical relaxation studies are carried out by impedance and modulus spectroscopy. Relaxation frequency is found to increase with temperature and MnO mol fraction. Electrical characterization predicts that these compounds have potentials for use as solid oxide fuel cell electrolyte material. (C) 2015 Elsevier Ltd. All rights reserved.

Optical and dielectric study of strontium modified barium zirconium titanate ceramic prepared by high energy ball milling

Strontium modified barium zirconium titanate with general formula Ba1-xSrxZr0.05Ti0.95O3 ceramics have been prepared by solid state and high energy ball milling technique. The X-ray diffraction and Rietveld refinement studies show that all the compositions have single phase symmetry. The composition BaZr0.05Ti0.95O3 shows orthorhombic symmetric with space group Amm2. The structure changes from orthorhombic to tetragonal with strontium doping up to x = 0.3 and with further addition, changes to cubic. The scanning electron micrographs show that the grain size decreases with increase in strontium content. The temperature dependent dielectric behavior shows three phase transition in the parent material which merges with an increase in Sr content The transition temperature and dielectric constant decreases with an increase in Sr concentration. The phase transition becomes more diffused with increment in doping concentration. The ferroelectric behavior of the ceramics is studied by the hysteresis loop. The optical behavior is studied by the UV-visible spectroscopy and found that the optical band gap increases with Sr concentration. (C) 2015 Elsevier B.V. All rights reserved.

On the Room Temperature Ferromagnetic and Ferroelectric Properties of Pb(Fe1/2Nb1/2)O-3

We report the origin of room temperature (RT) ferromagnetic and ferroelectric properties of Pb(Fe1/2Nb1/2)O-3 (PFN) ceramic sample prepared by modified solid-state reaction synthesis by a single-step method, based on X-ray diffraction (XRD), neutron diffraction (ND), Mossbauer spectroscopy and electron paramagnetic resonance (EPR) spectroscopy results. Formation of single-phase monoclinic PFN ceramic with Cm space group was confirmed by XRD and ND at RT. The morphology studied by scanning electron microscopy (SEM) confirmed uniform microstructure of the sample with average grain size of similar to 2 mu m. The ND, Mossbauer spectroscopy, M-H loop and EPR studies were carried out to confirm the existence of weak ferromagnetism at RT. A clear opening of hysteresis (M-H) loop is evidenced as the existence of weak ferromagnetism at RT. EPR spectrum clearly shows the ferromagnetism through a good resonance signal. The symmetric EPR line shape with g = 1.9895 observed in PFN sample was identified to be due to Fe3+ ions. Mossbauer spectroscopy at RT shows superparamagnetic behaviour with presence of Fe in 3+ valence state. Ferroelectric P-E loops on PFN at RT confirm the existing ferroelectric ordering. Our observation is in agreement with literature, and it supports that the origin of ferromagnetism and ferroelectricity is isolated, i.e. from different regions in the sample. Our results do not support the multiferroic nature of PFN at RT.

Origin of room temperature weak-ferromagnetism in antiferromagnetic Pb(Fe2/3W1/3)O-3 ceramic

We report the origin of room temperature weak ferromagnetic behavior of polycrystalline Pb(Fe2/3W1/3)O-3 (PFW) powder. The structure and magnetic properties of the ceramic powder prepared by a Columbite method were characterized by X-ray and neutron diffraction, Mossbauer spectroscopy and magnetization measurements. Rietveld analysis of diffraction data confirm the formation of single phase PFW, without traces of any parasitic pyrochlore phase. PFW was found to crystallize in the cubic structure at room temperature. The Rietveld refinement of neutron diffraction data measured at room temperature confirmed the G-type antiferromagnetic structure of PFW in our sample. However, along with the antiferromagnetic (AFM) ordering of the Fe spins, we have observed the existence of weak ferromagnetism at room temperature through: (i) a clear opening of hysteresis (M-H) loop, (ii) bifurcation of the field cooled and zero-field cooled susceptibility; supported by Mossbauer spectroscopy results. The P-E loop measurements showed a non-linear slim hysteresis loop at room temperature due to the electronic conduction through the local inhomogeneities in the PFW crystallites and the inter-particle regions. By corroborating all the magnetic measurements, especially the spin glass nature of the sample, with the conduction behavior of the sample, we report here that the observed ferromagnetism originates at these local inhomogeneous regions in the sample, where the Fe-spins are not perfectly aligned antiferromagnetically due to the compositional disordering. (C) 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Tuning of dielectric, pyroelectric and ferroelectric properties of 0.715Bi(0.5)Na(0.5)TiO(3)-0.065BaTiO(3)-0.22SrTiO(3) ceramic by internal clamping

This study systematically investigates the phenomenon of internal clamping in ferroelectric materials through the formation of glass-ceramic composites. Lead-free 0.715Bi(0.5)Na(0.5)TiO(3)-0.065BaTiO(3)-0.22SrTiO(3) (BNT-BT-ST) bulk ferroelectric ceramic was selected for the course of investigation. 3BaO - 3TiO(2) - B2O3 (BTBO) glass was then incorporated systematically to create sintered samples containing 0%, 2%, 4% and 6% glass (by weight). Upon glass induction features like remnant polarization, saturation polarization, hysteresis losses and coercive field could be varied as a function of glass content. Such effects were observed to benefit derived applications like enhanced energy storage density similar to 174 k J/m(3) to similar to 203 k J/m(3) and pyroelectric coefficient 5.7x10(-4) Cm-2K-1 to 6.8x10(-4) Cm-2K-1 by incorporation of 4% glass. Additionally, BNT-BT-ST depolarization temperature decreased from 457K to 431K by addition of 4% glass content. Glass incorporation could systematically increases diffuse phase transition and relaxor behavior temperature range from 70 K to 81K and 20K to 34 K, respectively when 6% and 4% glass content is added which indicates addition of glass provides better temperature stability. The most promising feature was observed to be that of dielectric response tuning. It can be also used to control (to an extent) the dielectric behavior of the host ceramic. Dielectric permittivity and losses decreased from 1278 to 705 and 0.109 to 0.107 for 6% glass, at room temperature. However this reduction in dielectric constant and loss increases pyroelectric figures of merit (FOMs) for high voltage responsivity (F-v) high detectivity (F-d) and energy harvesting (F-e) from 0.018 to 0.037 m(2)C(-1), 5.89 to 8.85 mu Pa-1/2 and 28.71 to 61.55 Jm(-3)K(-2), respectively for 4% added ceramic-glass at room temperature. Such findings can have huge implications in the field of tailoring ferroelectric response for application specific requirements. (C) 2015 Author(s).

Performance analysis of 1200 kV ceramic disc insulator string under normal and faulted conditions

In the recent years there has been a considerable increase in demand for the electrical power requirement in our country. Presently the transmission system voltages has increased to 765 kV ac and 800kV dc, keeping in view of the future demand experimentation and simulation studies for 1200 kV ac and 1100kV dc transmission are under progress. In the present study an attempt is made to compute the surface potential, electric field across the string of ceramic disc insulators used for 1200kV ac systems. The studies are carried out under normal, polluted conditions and for the case of insulator string containing faulty discs. A computer code using surface charge simulation method (SCSM) is developed for the present analysis. Also a new technique which enhances the surface potential and electric field strength for the existing ceramic disc insulators is presented.

A novel in-situ polymer derived nano ceramic MMC by friction stir processing

Fiction stir processing (FSP) is a solid state technique used for material processing. Tool wear and the agglomeration of ceramic particles have been serious issues in FSP of metal matrix composites. In the present study, FSP has been employed to disperse the nanoscale particles of a polymer-derived silicon carbonitride (SiCN) ceramic phase into copper by an in-situ process. SiCN cross linked polymer particles were incorporated using multi-pass ESP into pure copper to form bulk particulate metal matrix composites. The polymer was then converted into ceramic through an in-situ pyrolysis process and dispersed by ESP. Multi-pass processing was carried out to remove porosity from the samples and also for the uniform dispersion of polymer derived ceramic particles. Microstructural observations were carried out using Field Emission Scanning Electron Microscopy (FE-SEM) and Transmission Electron Microscopy (TEM) of the composite. The results indicate a uniform distribution of similar to 100 nm size particles of the ceramic phase in the copper matrix after ESP. The nanocomposite exhibits a five fold increase in microhardness (260HV(100)) which is attributed to the nano scale dispersion of ceramic particles. A mechanism has been proposed for the fracturing of PDC particles during multi pass FSP. (C) 2015 Elsevier Ltd. All rights reserved

Volume change behavior of lime treated gypseous soil - influence of mineralogy and microstructure

Series of oedometer tests and micro-analytical studies (XRD, SEM and EDAX) have been carried out to investigate the influence of varying gypsum content on swell, compressibility and permeability of lime treated montmorillonitic soil after curing for different period. Immediate swell is observed on inundation of compacted samples with water and continuously increased with gypsum content. However, changes in swell are found to be marginal with curing. This is attributed to the formation and growth of ettringite crystals by ionic reactions of aluminum calcium-sulfate in the presence of water which is confirmed through detailed micro-analysis. The higher swell in uncured specimens and gradual reduction in swell with increase in curing periods are due to relative dominance of formation and growth of ettringite and cementitious compounds, respectively. Also, the ionic reaction products are found to bear a significant influence on the compressibility and permeability behavior. (C) 2015 Elsevier B.V. All rights reserved.

Microstructure Formation in Dissimilar Metal Welds: Electron Beam Welding of Ti/Ni

We present results for electron beam welding of a binary Ti/Ni dissimilar metal couple. The difference in physical properties of the base metals and metallurgical features (thermodynamics and kinetics) of the system influence both macroscopic transport and microstructure development in the weld. Microstructures near the fusion interfaces are markedly different from those inside the weld region. At the Ti side, Ti2Ni dendrites are observed to grow toward the fusion interface, while in the Ni side, layered growth of gamma-Ni, Ni3Ti, and Ni3Ti + NiTi eutectic is observed. Different morphologies of the latter eutectic constitute the predominant microstructure inside the weld metal region. These results are compared and contrasted with those from laser welding of the same binary couple, and a scheme of solidification is proposed to explain the observations. This highlights notable departures from welding of similar and other dissimilar metals such as a significant asymmetry in heat transport that governs progress of solidification from each side of the couple, and a lack of unique liquidus isotherm characterizing the liquid-solid front.

Evolution of Texture and Microstructure in Deformed and Annealed Copper-Iron Multilayer

The effect of multiple phases on the evolution of texture during cold rolling and annealing of a copper-iron multilayer, fabricated by accumulative roll bonding, has been studied. The presence of an iron layer affects the deformation texture of the copper layer only at very large strains. On the other hand, a strong effect of copper on iron is observed at both small and large strains. At smaller strains, the larger deformation carried by the copper suppresses the texture development in the iron, whereas, at higher strains, selection of specific orientation relationship at the interface influences the texture of the iron layer. Shear banding and continuous dynamic recrystallization were found to influence the evolution of texture in the copper layer. The influence of large plastic deformation on the recrystallization behavior of copper is demonstrated with the suppression of typical fcc annealing texture components, described as constrained recrystallization. Evolution of typical annealing texture component is suppressed because of the multilayer microstructure. The plane of the interface formed during deformation is determined by a combination of the rolling texture of individual phases, constrained annealing, and the tendency to form a low-energy interface between the two phases during annealing.

Designing Novel Sulphate-based Ceramic Materials as Insertion Host Compounds for Secondary Batteries

Rechargeable batteries have propelled the wireless revolution and automobiles market over the past 25 years. Developing better batteries with improved energy density demands unveiling of new cathode ceramic materials with suitable diffusion channels and open framework structure. In this pursuit of achieving higher energy density, one approach is to realize enhanced redox voltage of insertion of ceramic compounds. This can be accomplished by incorporating highly electronegative anions in the cathode ceramics. Building on this idea, recently various sulphate- based compounds have been reported as high voltage cathode materials. The current article highlights the use of sulphate (SO4) based cathodes to realize the highest ever Fe3+/Fe2+ redox potentials in Li-ion batteries (LiFeSO4F fluorosulphate: 3.9V vs Li/Li+) and Na-ion batteries (Na2Fe2(SO4)(3) polysulphate: 3.8V vs Na/Na+). These sulphate-based cathode ceramic compounds pave way for newer avenues to design better batteries for future applications.

Effect of current density on the microstructure and corrosion properties of plasma electrolytic oxidation (PEO) coatings on AM50 Mg alloy produced in an electrolyte containing clay additives

Plasma electrolytic oxidation coatings were produced on AM50 Mg alloy in alkaline phosphate based electrolyte with montmorillonite clay additives employing current densities of 30, 60, and 120 mA/cm(2). The effect of current density on the microstructure and corrosion properties of the coating was investigated. The clay additives got melted and reactively incorporated into the coating forming an amorphous phase, at all the current densities. However, the coating was predominantly amorphous only at 30 mA/cm(2) and with increasing current density, increasing fractions of crystalline phases were formed. Higher current densities resulted in increased thickness of the coating, but reduced the compactness of the coatings. Electrochemical impedance spectroscopy tests in 0.5 wt.% (0.08 M) and 3.5 wt.% (0.6 M) NaCl solution revealed that the coatings processed at 30 mA/cm(2) exhibited a relatively better initial corrosion resistance owing to its relatively defect-free barrier layer and compactness of the coating. However, the presence of amorphous phases in significant amounts and lack of MgO in the coating resulted in increased rate of dissolution of the coatings and degradation of corrosion resistance. Coatings produced at higher current densities exhibited initial inferior corrosion resistance due to a more defective barrier layer and increased porosity in pore band and outer porous layer. However, the increased amount of crystalline phases and an increased amount of MgO, which resisted dissolution, counterbalanced the negative effects of defective barrier and increased porosity resulting in a relatively lower rate of the degradation of the corrosion resistance. Thus, the corrosion resistance of all the coatings continuously decreased with time and became similar after prolonged immersion in NaCl solution. Increasing current density, therefore, did not prove to be beneficial for the improvement of the corrosion performance of the PEO coatings. (C) 2016 Elsevier B.V. All rights reserved.

Primary and rechargeable zinc-air batteries using ceramic and highly stable TiCN as an oxygen reduction reaction electrocatalyst

Primary and secondary zinc-air batteries based on ceramic, stable, one dimensional titanium carbonitride (TiCN) nanostructures are reported. The optimized titanium carbonitride composition by density functional theory reveals their good activity towards the oxygen reduction reaction (ORR). Electrochemical measurements show their superior performance for the ORR in alkaline media coupled with favourable kinetics. The nanostructured TiCN lends itself amenable to be used as an air cathode material in primary and rechargeable zinc-air batteries. The battery performance and cyclability are found to be good. Further, we have demonstrated a gel-based electrolyte for rechargeable zinc-air batteries based on a TiCN cathode under ambient, atmospheric conditions without any oxygen supply from a cylinder. The present cell can work at current densities of 10-20 mA cm(2) (app. 10 000 mA g(-1) of TiCN) for several hours (63 h in the case of 10 mA cm(-2)) with a charge retention of 98%. The low cost, noble metal-free, mechanically stable and corrosion resistant TiCN is a very good alternative to Pt for metal-air battery chemistry.