Structural and relaxor characteristics of Ca0.18Sr0.226Ba0.594Nb2O6

Polycrystalline Ca0.18Sr0.226Ba0.594Nb2O6 (CSBN18) was synthesized via the solid-state reaction route. X-ray structural studies confirmed it belonged to the tetragonal tungsten bronze family. Rietveld refinement of the X-ray data has been carried out for CSBN18 where the atomic positions and site occupancy factors for A-sites have been determined. The dielectric properties of CSBN18 ceramic were studied as a function of temperature in the 100 Hz - 1 MHz frequency range. The dielectric relaxation followed the Vogel-Fulcher relation wherein E-a = 37.4 meV; T-f = 131.5 degrees C and omega(0) = 4.31 x 10(9) rad s(-1). A high pyroelectric coefficient of similar to 250 mu C m(-2).K was obtained around the transition temperature (similar to 150 degrees C). This is significantly higher than that reported for polycrystalline SrxBa1-xNb2O6 (SBN). However, the piezoelectric coefficient (d(33)) of the title composition was as low as 6 pC N-1.

Ferroelectric and optical properties of Ba5Li2Ti2Nb8O30 ceramics potential for memory applications

Giant grained (42 mu m) translucent Ba5Li2Ti2Nb8O30 ceramic was fabricated by conventional sintering technique using the powders obtained via solid state reaction route. These samples were confirmed to possess tetragonal tungsten bronze structure (P4bm) at room temperature. The scanning electron microscopy established the average grain size to be close to 20 mu m. The photoluminescence studies carried out on these ceramics indicated sharp emission bands around 433 and 578 nm at an excitation wavelength of 350 nm which were attributed to band-edge emission as the band gap was 2.76 eV determined by Kubelka-Munk function. The dielectric properties of these ceramics were studied over wide frequency range (100-1 MHz) at room temperature. The decrease in dielectric constant with frequency could be explained on the basis of Koops theory. The dielectric constant and the loss were found to decrease with increasing frequency. The Curie temperature was confirmed to be similar to 370 A degrees C based on the dielectric anomaly observed when these measurements were carried out over a temperature range of 30-500 A degrees C. This shows a deviation from Curie-Weiss behaviour and hence an indicator of the occurrence of disordering in the system, the gamma = 1.23 which confirms the diffuse ferroelectric transition. These ceramics at room temperature exhibited P-E hysteresis loops, though not well saturated akin to that of their single crystalline counterparts. These are the suitable properties for ferroelectric random access memory applications.

The use of tin and bronze in prehistoric southern Indian metallurgy

The medieval icons of southern India are among the most acclaimed Indian artistic innovations, especially those of the Chola Tamil kingdom (9th–10th centuries), which is best known for the Hindu iconography of the Dance of Siva that captured the imagination of master sculptor Rodin.1 Apart from these prolific images, however, not much was known about southern Indian copperbased metallurgy. Hence, these often spectacular castings have been regarded as a sudden efflorescence, almost without precedent, of skilled metallurgy as contrasted with tin-rich China or southeast Asia, for instance, where a developed copper-bronze tradition has been better appreciated.

Competing tetragonal and monoclinic phases in Ni2.2Mn0.80Ga

Temperature dependent synchrotron x-ray powder diffraction, differential scanning calorimetry, and magnetic measurements were performed on Ni2+xMn1-xGa (x=0.20 and 0.35) magnetic shape memory alloys. For x=0.20, though the monoclinic phase is thermodynamically stable, a trace of residual stress can stabilize a tetragonal phase. The residual-stress-induced tetragonal phase transforms to the cubic austenite phase over an unusually large temperature range (348 K < T < 693 K), suggesting extremely slow kinetics of transformation. In contrast to x=0.20, the thermodynamically stable phase of x=0.35 is tetragonal and this composition exhibits the usual features of a reversible martensitic transformation. The results suggest that for x=0.20 the monoclinic and tetragonal phases are nearly degenerate.

Diffusion and Creep in Silica-Doped Tetragonal Zirconia

Silica segregation at two grain junctions or in amorphous triple junction pockets can influence creep by altering the grain-boundary diffusion coefficient. Although the addition of silica to superplastic yttria-stabilized tetragonal zirconia enhances ductility, differences in reported creep parameters have limited critical identification of rate controlling mechanisms. The present study on a pure 3 mol% yttria-stabilized tetragonal zirconia (3YTZ) and 3YTZ with 0.39 or 3.9 wt% silica involved a detailed characterization of creep over a wide range of experimental conditions and also tracer diffusion measurements. The data broadly show transitions in creep stress exponents from n∼1 to ∼2 to ∼3 with a decrease in the stress. The data at high stresses are consistent with Coble diffusion creep, and creep at lower stresses is attributed to interface-controlled diffusion creep. Measurements indicated that silica does not have any significant influence on grain boundary or lattice diffusion, and this is consistent with the observation that 3YTZ and 3YTZ with 0.39% or 3.9% silica exhibit essentially identical creep behavior in the Coble creep regime. Silica influences the interface control process so that the transitions in stress exponents are pushed to lower stresses with an increase in silica content.

Temperature dependence of g values in tetragonal ionic Cu++ salts

A temperature dependence has been observed in the spin-Hamiltonian parameters of the Cu++ ion in a tetragonal crystal field and the variation has been interpreted in terms of vibronic effects.

Unconventional mechanism of stabilization of a tetragonal phase in the perovskite ferroelectric (PbTiO3)(1-x)(BiFeO3)(x)

Temperature-dependent x-ray powder-diffraction study of the tetragonal compositions of PbTiO3-BiFeO3 series has revealed that, unlike for all the known ferroelectric perovskites, the compositions exhibiting giant tetragonality is stabilized from the cubic phase via a complex transition pathway which involve (i) formation of minor monoclinic phase with a large pseudotetragonality along with an intermediate tetragonal phase (major) with a small tetragonality, (ii) gradual vanishing of the intermediate tetragonal phase and concomitant increase in the monoclinic regions, and finally (iii) gradual transformation of the monoclinic phase to the tetragonal phase with giant tetragonality.The system seems to adopt such a complex transition pathway to create amicrostructure with very large number of domains and interfaces for stress relief, which would not have been possible in case of a direct cubic-tetragonal transition.

Phase Transformation Introduced by Mechanical and Chemical Surface Preparations of Tetragonal Zirconia Polycrystals

Cutting of Y2O3-doped TZP rods by a low-speed diamond saw introduces an unidentified, metastable phase X (x-ZrO2) coexisting with the tetragonal (t-ZrO2) and the monoclinic (m-ZrO2) phases initially present in the sample. Further mechanical deformation of the cut surface by indentation or polishing sustains the x-ZrO2. Chemical etching removes the x-ZrO2 and increases the m-ZrO2content.

The mechanical response of tetragonal zirconia polycrystal to conical indentation

Blocks of 3Y-TZP were indented with conical diamond indenters. indentation caused tetragonal to monoclinic phase transformation in a subsurface. Of the cracks generated in the subsurface, radial and lateral cracks can be accounted for by a continuum model of the indented subsurface, built using a combination of the Boussinesq and blister stress fields. Additional ring, median and cone cracks were also observed. It is hypothesized that the latter are motivated by the reduction in blister strength or residual energy brought about by the material damage caused by the phase transformation. This damage reduces the load bearing capacity of the material progressively with increasing normal load.

Surface damage of yttria-tetragonal zirconia polycrystals and magnesia-partially-stabilized zirconia in single-point abrasion

Commercially available 3Y-TZP and Mg-PSZ flats mere abraded by a 150 degrees diamond cone at -196 degrees, 25 degrees, 200 degrees, and 400 degrees C. The coefficient of friction, the track width, and the morphological features of the track were recorded. Raman spectroscopy mas used to record the tetragonal-to-monoclinic phase transformation (t --> m) as a function of distance away from the track. The study was undertaken to establish the influence of tangential traction on phase transformation and surface damage.

Amorphous, Monoclinic, and Tetragonal Porous Zirconia Through a Controlled Self-Sustained Combustion Route

Porous, large surface area, metastable zirconias, are of importance to catalytic, electrochemical, biological, and thermal insulation applications. Combustion synthesis is a very commonly used method for producing such zirconias. However, its rapid nature makes control difficult. A simple modification has been made to traditional solution combustion synthesis to address this problem. It involves the addition of starch to yield a starting mixture with a ``dough-like'' consistency. Just 5 wt% starch is seen to significantly alter the combustion characteristics of the ``dough.'' In particular, it helps to achieve better control over reaction zone temperature that is significantly lower than the one calculated by the adiabatic approximation typically used in self-propagating high-temperature synthesis. The effect of such control is demonstrated by the ability to tune dough composition to yield zirconias with different phase compositions from the relatively elusive ``amorphous'' to monoclinic (> 30 nm grain size) and tetragonal pure zirconia (< 30 nm grain size). The nature of this amorphous phase has been investigated using infrared spectroscopy. Starch content also helps tailor porosity in the final product. Zirconias with an average pore size of about 50 mu m and specific surface area as large as 110 m2/g have been obtained.

Analysis of deformation mechanisms in superplastic yttria-stabilized tetragonal zirconia

There have been extensive experimental observations of changes in the apparent rate controlling creep parameters in studies on superplastic materials. The three most common explanations associated with these changes in the stress exponent, n, the activation energy Q and the inverse grain size exponent, p involve the effect of concurrent grain growth, the operation of a threshold stress or transitions in creep mechanisms. Each of these factors may influence experimental creep data in a similar manner. Therefore, a careful analysis of the consequences of all three factors must involve the development of a consistent set of experimental observations in order to adequately distinguish the effects of each. This paper discusses the role of concurrent grain growth, a threshold stress and transitions in creep mechanisms in superplastic materials. Specific attention is given to the analysis of data on superplastic yttria-stabilized zirconia ceramics for which an increase in n has been observed at low applied stresses. It is demonstrated that neither concurrent grain growth nor a threshold stress can account for all the relevant experimental observations in this material. It is concluded that the changes in rate controlling creep parameters are associated with the operation of two distinct sequential mechanisms as part of a grain boundary sliding process.

The Archaeometallurgical Implications of New Findings of Traditional Crafts of Making High Tin ‘Delta’ Bronze Mirrors and ‘Beta’ Bronze Vessels in Kerala State of South India

New metallurgical and ethnographic observations of the traditional manufacture of specular high-tin bronze mirrors in Kerala state of southern India are discussed, which is an exceptional example of a surviving craft practice of metal mirror-making in the world. The manufacturing process has been reconstructed from analytical investigations made by Srinivasan following a visit late in 1991 to a mirror making workshop and from her technical studies of equipment acquired by Glover in March 1992 from another group of mirror makers from Pathanamthita at an exhibition held at Crafts Museum, Delhi. Finished and unfinished mirror from two workshops were of a binary, copper-tin alloy of 33% tin which is close to the composition of pure delta phase, so that these mirrors are referred to here as ‘delta’ bronzes. For the first time, metallurgical and field observations were made by Srinivasan in 1991 of the manufacture of high-tin ‘beta’ bonze vessels from Palghat district, Kerala, i‥e of wrought and quenched 23% tin bronze. This has provided the first metallurgical record for a surviving craft of high-tin bronze bowl making which can be directly related to archaeological finds of high-tin bronze vessels from the Indian subcontinent and Southeast Asia. New analytical investigations are presented of high-tin beta bronzes from the Indian subcontinent which are some of the earliest reported worldwide. These coupled with the archaeometallurgical evidence suggests that these high-tin bronze techniques are part of a long, continuing, and probably indigenous tradition of the use of high-tin bronzes in the Indian subcontinent with finds reported even from Indus Valley sites. While the source of tin has been problematic, new evidence on bronze smelting slags and literary evidence suggests there may have been some sources of tin in South India.

Gibbs’ energy of formation of YBa2Cu3O7-x (tetragonal)

The high temperature ceramic oxide superconductor YBa2Cu3O7-x (1–2–3 compound) is generally synthesized in an oxygen-rich environment. Hence any method for determining its thermodynamic stability should operate at a high oxygen partial pressure. A solid-state cell incorporating CaF2 as the electrolyte and functioning under pure oxygen at a pressure of 1·01 × 105 Pa has been employed for the determination of the Gibbs’ energy of formation of the 1–2–3 compound. The configuration of the galvanic cell can be represented by: Pt, O2, YBa2Cu3O7−x , Y2BaCuO5, CuO, BaF2/CaF2/BaF2, BaZrO3, ZrO2, O2, Pt. Using the values of the standard Gibbs’ energy of formation of the compounds BaZrO3 and Y2BaCuO5 from the literature, the Gibbs’ energy of formation of the 1–2–3 compound from the constituent binary oxides has been computed at different temperatures. The value ofx at each temperature is determined by the oxygen partial pressure. At 1023 K for O content of 6·5 the Gibbs’ energy of formation of the 1–2–3 compound is −261·7 kJ mol−1.

Temperature dependent photoemission spectroscopy on lightly-doped sodium tungsten bronze

Temperature dependent photoemission studies on lightly doped (x = 0.025) sodium tungsten bronzes, NaxWO3 have been investigated by high-resolution photoemission spectroscopy. The experimental results show evidence for polaron formation at the valence band edge and the photoemission spectra taken in different modes of the electron analyzer suggest that the density of states at the valence band edge gradually moves to other k-points in the Brillouin zone with increasing temperature and explain the dynamics of polarons in the insulating disordered sodium tungsten bronzes. (C) 2012 Elsevier Ltd. All rights reserved.