Influence of sintering conditions and doping on the dielectric relaxation originating from the surface layer effects in CaCu3Ti4O12 ceramics

Detailed investigations into the dielectric dispersion phenomenon in the giant dielectric constant material CaCu3Ti4O12 (CCTO) around room temperature revealed the existence of two successive dielectric relaxations. In the temperature domain, a new dielectric relaxation was clearly observed around 250K, in addition to the well-investigated dielectric relaxation close to 100K. The effect of sintering and doping (La3+) on the strength of these dielectric relaxations were studied in detail. The sintering temperature as well as its duration was found to have tremendous influence on the dielectric relaxation that was encountered around 250 K. This Maxwell-Wagner (M-W) type of relaxation was found to be originating from the surface layer containing the Cu-rich phase, which was ascribed to the difference in the oxygen content between the surface and the interior of the sample. Interestingly, this particular additional relaxation was not observed in La2/3Cu3Ti4O12, a low dielectric constant member of the CCTO family, in which the segregation of Cu-rich phase on the surface was absent. Indeed the correlation between the new relaxation and the presence of Cu-rich phase in CCTO ceramics was further corroborated by the absence of the same after removing the top and bottom layers. (C) 2007 Elsevier Ltd. All rights reserved.

Synthesis, structure and magnetic behavior of a new three-dimensional Manganese phosphite-oxalate: [C2N2H10][Mn-2(II)(OH2)(2)(HPO3)(2)(C2O4)]

A novel manganese phosphite-oxalate, [C2N2H10][Mn-2(II)(OH2)(2)(HPO3)(2)(C2O4)] has been hydothermally synthesized and its structure determined by single-crystal X-ray diffraction. The structure consists of neutral manganese phosphite layers, [Mn(HPO3)](infinity), formed by MnO6 octahedra and HPO3 units, cross-linked by the oxalate moieties. The organic cations occupy the middle of the 8-membered one dimensional channels. Magnetic studies indicate weak antiferromagnetic interactions between the Mn2+ ions. (C) 2009 Elsevier Inc. All rights reserved.

The effects of manganese content and mould size on abrasion and slurry erosion behaviour of chromium-manganese iron systems investigated by positron lifetime spectroscopy

Abrasion and slurry erosion behaviour of chromium-manganese iron samples with chromium (Cr) in the range similar to 16-19% and manganese (Mn) at 5 and 10% levels have been characterized for hardness followed by microstructural examination using optical and scanning electron microscopy. Positron lifetime studies have been conducted to understand the defects/microporosity influence on the microstructure. The samples were heat treated and characterized to understand the structural transformations in the matrix. The data reveals that hardness decreased with increase in Mn content from 5 to 10% in the first instance and then increase in the section size in the other case, irrespective of the sample conditions. The abrasion and slurry erosion losses show increase with increase in the section size as well as with increase in Mn content. The positron results show that as hardness increases from as-cast to heat treated sample, the positron trapping rate and hence defect concentration showed opposite trend as expected. So a good correlation between defects concentration and the hardness has been observed. These findings also corroborate well with the microstructural features obtained from optical and scanning electron microscopy. (C) 2009 Elsevier B. V. All rights reserved.

The effect of pressure and W-doping on the properties of ZnO thin films for NO2 gas sensing

Pure and W-doped ZnO thin films were obtained using magnetron sputtering at working pressures of 0.4 Pa and 1.33 Pa. The films were deposited on glass and alumina substrates at room temperature and subsequently annealed at 400oC for 1 hour in air. The effects of pressure and W-doping on the structure, chemical, optical and electronic properties of the ZnO films for gas sensing were examined. From AFM, the doped film deposited at higher pressure (1.33 Pa) has spiky morphology with much lower grain density and porosity compared to the doped film deposited at 0.4 Pa. The average gain size and roughness of the annealed films were estimated to be 65 nm and 2.2 nm, respectively with slightly larger grain size and roughness appeared in the doped films. From XPS the films deposited at 1.33 Pa favored the formation of adsorbed oxygen on the film surface and this has been more pronounced in the doped film which created active sites for OH adsorption. As a consequence the W-doped film deposited at 1.33 Pa was found to have lower oxidation state of W (35.1 eV) than the doped film deposited at 0.4 Pa (35.9 eV). Raman spectra indicated that doping modified the properties of the ZnO film and induced free-carrier defects. The transmittance of the samples also reveals an enhanced free-carrier density in the W-doped films. The refractive index of the pure film was also found to increase from 1.7 to 2.2 after W-doping whereas the optical band gap only slightly increased. The W-doped ZnO film deposited at 0.4 Pa appeared to have favorable properties for enhanced gas sensing. This film showed significantly higher sensing performance towards 5-10 ppm NO2 at lower operating temperature of 150oC most dominantly due to increased free-carrier defects achieved by W-doping.

Morphological differentiation observed in manganese oxidizing bacterial colonies

Bacteria play a vital role in bringing about Mn(II) oxidation in the natural environment. A study was conducted to identify the potential threat offered by these bacteria in bringing about biomineralisation of manganese dioxide on titanium surfaces exposed to seawater. During the study it was observed that the bacteria such as Pseudomonas and Bacillus formed brown colonies on agar plates amended with Mn2+ indicating their ability to oxidize Mn(II). These colonies showed distinct morphologies when grown on plates containing Mn(II) while they formed normal colonies in the absence of Mn.(II).Hence it is possible that these morphologically distinct structures produced by the bacterial colonies assist these bacteria to perform this function of Mn-oxidation.

Theory of the unusual doping and temperature dependence of photoemission spectra in manganites

A recent, major, puzzle in the core-level photoemission spectra of doped manganites is the observation of a 1–2 eV wide shoulder with intensity varying with temperature T as the square of the magnetization over a T scale of order 200 K, an order of magnitude less than electronic energies. This is addressed and resolved here, by extending a recently proposed two-fluid polaron–mobile electron model for these systems to include core-hole effects. The position of the shoulder is found to be determined by Coulomb and Jahn-Teller energies, while its spectral weight is determined by the mobile electron energetics which is strongly T and doping dependent, due to annealed disorder scattering from the polarons and the t2g core spins. Our theory accounts quantitatively for the observed T dependence of the difference spectra, and furthermore, explains the observed correspondence between spectral changes due to increasing doping and decreasing T.

Spectroscopic ellipsometry investigations of the optical properties of manganese doped bismuth vanadate thin films

The optical properties of Bi(2)V(1-x)MnxO(5.5-x) (x=0.05, 0.1, 0.15 and 0.2 at.%) thin films fabricated by pulsed laser deposition on platinized Silicon Substrates were Studied in UV-visible spectral region (1.51-4.17 CV) using spectroscopic ellipsometry. The optical constants and thicknesses of these films have been obtained by fitting the ellipsometric data (Psi and Delta) using a multilayer four-phase model system and a relaxed Lorentz oscillator dispersion relation. The surface roughness and film thickness obtained by spectroscopic ellipsometry were found to be consistent with the results obtained by atomic force and scanning electron microscopy. The refractive index measured at 650 nm does not show any marginal increase with Mn content. Further, the extinction coefficient does not show much decrease with increasing Mn content. An increase in optical band gap energy from 2.52 to 2.77 eV with increasing Mn Content from x = 0.05 to 0.15 was attributed to the increase in oxygen ion vacancy disorder. (C) 2009 Elsevier Ltd. All rights reserved.

New benzidine procedure for determination of manganese in biological samples

A simple and accurate method for the determination of 0.25 to 1.0 μg. of manganese (in samples containing 1 to 4 μg. of manganese) has been developed by modifying the conditions for the reaction between permanganate and benzidine. Manganese is oxidized with potassium periodate in orthophosphoric acid and selectively estimated in the presence of excess oxidant with benzidine in formic acid. The procedure is applicable for estimation of manganese in biological samples, with recoveries in the range 97.5 to 106.1%.

Iron and manganese in groundwater in Finland : Occurrence in glacifluvial aquifers and removal by biofiltration

Yhteenveto: Rauta ja mangaani Suomen glasifluviaalisten akviferien pohjavedessä ja poisto biosuodatuksella

Low-temperature polymer precursor-based synthesis of nanocrystalline particles of lanthanum calcium manganese oxide (La0.67Ca0.33MnO3) with enhanced ferromagnetic transition temperature

We report a simple modified polymeric precursor route for the synthesis of highly crystalline and homogenous nanoparticles of lanthanum calcium manganese oxide (LCMO). The LCMO phase formation was studied by thermal analysis, x-ray powder diffraction, and infrared spectroscopy at different stages of heating. These nanocrystallites (average particle size of 30 nm) possess ferromagnetic-paramagnetic transition temperature (T-c) of 300 K, nearly 50 K higher than that of a single crystal. The Rietveld analysis of the powder x-ray diffraction data of the nanopowders reveals significant lattice contraction and reduction in unit cell anisotropy-these structural changes are correlated to the enhancement in T-c.

Manganese-mediated ferromagnetism in La2Fe1-xMn2xCr1-xO6 perovskite oxides

We have investigated the structure and magnetic properties of the perovskite oxides of the formula La2Fe1-xMn2xCr1-xO6 (0 < x < 1.0). For 0 < x <= 0.5, the members adopt the orthorhombic (Pbnm) structure, where the transition metal atoms are disordered at the 4b sites and the MO6 (M = Fe, Mn, Cr) octahedra become increasingly distorted with increasing x. For 0.65 <= x < 1.0, the members adopt the rhombohedral (R-3c) structure that is similar to LaMnO3+delta (delta >= 0.1) where the MO6 octahedra are undistorted. While the magnetic properties of the latter series are largely similar to the parent LaMnO3+delta arising from the double-exchange (DE) between mixed valent Mn-III/Mn-IV, the magnetic properties of the orthorhombic members show a distinct (albeit weak) ferromagnetism (T-C similar to 200 K) that seems to arise from a Mn-III-mediated superexchange (SE) between Fe-III/Cr-III in the disordered perovskite structure containing Fe-III, Mn-III and Cr-III.