Low temperature synthesis of pure cubic ZrO2 nanopowder: Structural and luminescence studies

Pure cubic zirconia (ZrO2) nanopowder is prepared for the first time by simple low temperature solution combustion method without calcination. The product is characterized by Powder X-ray Diffraction (PXRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Fourier Transform Infra Red spectroscopy (FTIR) and Ultraviolet-Visible spectroscopy (UV-Vis). The PXRD showed the formation of pure stable cubic ZrO2 nanopowders with average crystallite size ranging from 6 to 12 nm. The lattice parameters were calculated from Rietveld refinement method. SEM micrograph shows fluffy, mesoporous, agglomerated particles with large number of voids. TEM micrograph shows honey comb like arrangement of particles with particle size similar to 10 nm. The PL emission spectrum excited at 210 nm and 240 nm consists of intense bands centered at similar to 365 and similar to 390 nm. Both the samples show shoulder peak at 420 nm, along with four weak emission bands at similar to 484, similar to 528, similar to 614 and similar to 726 nm. TL studies were carried out pre-irradiating samples with gamma-rays ranging from 1 to 5 KGy at room temperature. A well resolved glow peak at 377 degrees C is recorded which can be ascribed to deep traps. With increase in gamma radiation there is linear increase in TL intensity which shows the possible use of ZrO2 as dosimetric material. (C) 2013 Elsevier B.V. All rights reserved.

Dielectric relaxation and anti-ferromagnetic coupling of BiEu03 and BiGd03

BiEuO3 (BE) and BiGdO3 (BG) are synthesized by the solid-state reaction technique. Rietveld refinement of the X-ray diffraction data shows that the samples are crystallized in cubic phase at room temperature having Fm3m symmetry with the lattice parameters of 5.4925(2) and 5.4712(2) A for BE and BG, respectively. Raman spectra of the samples are investigated to obtain the phonon modes of the samples. The dielectric properties of the samples are investigated in the frequency range from 42 Hz to 1.1 MHz and in the temperature range from 303 K to 673 K. An analysis of the real and imaginary parts of impedance is performed assuming a distribution of relaxation times as confirmed by the Cole-Cole plots. The frequency-dependent maxima in the loss tangent are found to obey an Arrhenius law with activation energy similar to 1 eV for both the samples. The frequency-dependent electrical data are also analyzed in the framework of conductivity formalism. Magnetization of the samples are measured under the field cooled (EC) and zero field cooled (ZFC) modes in the temperature range from 5 K to 300 K applying a magnetic Field of 500 Oe. The FC and ZFC susceptibilities show that BE is a Van Vleck paramagnetic material with antiferromagnetic coupling at low temperature whereas BG is an anti-ferromagnetic system. The results are substantiated by the M-11 loops of the materials taken at 5 K in the ZFC mode. (C) 2014 Elsevier B.V. All rights reserved

Green colored nano-pigments derived from Y2BaCuO5: NIR reflective coatings

A green colored nano-pigment Y2BaCuO5 with impressive near infra-red (NIR) reflectance (61% at 1100 nm) was synthesized by a nano-emulsion method. The developed nano-crystalline powders were characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), UV-vis-NIR diffuse reflectance spectroscopy and CIE-L*a*b* 1976 color scales. The XRD and Rietveld analyses of the designed pigment powders reveal the orthorhombic crystal structure for Y2BaCuO5, where yttrium is coordinated by seven oxygen atoms with the local symmetry of a distorted trigonal prism, barium is coordinated by eleven oxygen atoms, and the coordination polyhedron of copper is a distorted square pyramid CuO5]. The UV-vis spectrum of the nano-pigment exhibits an intense d-d transition associated with CuO5 chromophore between 2.1 and 2.5 eV in the visible domain. Therefore, a green color has been displayed by the developed nano-pigment. The potential utility of the nano-pigments as ``Cool Pigments'' was demonstrated by coating on to a building roofing material like cement slab and PVC coatings. (C) 2014 Elsevier Ltd. All rights reserved.

Effect of Zn substitution on the structural and magnetic properties of Ni-Co ferrites

A series of ferrite samples with the compositional formula, Ni0.5Co0.5-xZnxFe2O4 (0 <= x <= 0.5), was prepared using the citrate based sol gel method for the better understanding of zinc doping on the structural and magnetic properties. The Rietveld-refined X-ray diffraction data revealed that the samples are having cubic structure with the Fd-3m space group. The lattice parameter increased linearly with increasing Zn content. The surface morphology and stoichiometric ratio of the compositional elements were analyzed by scanning electron microscopy equipped with energy dispersive spectroscopy (EDS). EDS showed that the elemental ratios were stoichiometric. An examination of the magnetic properties revealed an increase in saturation magnetization with increasing Zn concentration up to x=0.3 and a decrease thereafter. These results could be explained using Neel's collinear two-sub-lattice model and three-sub-lattice non-collinear model suggested by Yafet and Kittel. The magnetic cubic anisotropy constant determined by the law of approach to saturation decreased with increasing Zn content. The underlying mechanism behind observed behavior was discussed qualitatively. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Thermoelectric Properties of Two-Phase PbTe with Indium Inclusions

The thermoelectric figure of merit (zT) can be increased by introduction of additional interfaces in the bulk to reduce the thermal conductivity. In this work, PbTe with a dispersed indium (In) phase was synthesized by a matrix encapsulation technique for different In concentrations. x-Ray diffraction analysis showed single-phase PbTe with In secondary phase. Rietveld analysis did not show In substitution at either the Pb or Te site, and this was further confirmed by room-temperature Raman data. Low-magnification (similar to 1500x) scanning electron microscopy images showed micrometer-sized In dispersed throughout the PbTe matrix, while at high magnification (150,000x) an agglomeration of PbTe particles in the hot-pressed samples could be seen. The electrical resistivity (rho) and Seebeck coefficient (S) were measured from 300 K to 723 K. Negative Seebeck values showed all the samples to be n-type. A systematic increase in resistivity and higher Seebeck coefficient values with increasing In content indicated the role of PbTe-In interfaces in the scattering of electrons. This was further confirmed by the thermal conductivity (kappa), measured from 423 K to 723 K, where a greater reduction in the electronic as compared with the lattice contribution was found for In-added samples. It was found that, despite the high lattice mismatch at the PbTe-In interface, phonons were not scattered as effectively as electrons. The highest zT obtained was 0.78 at 723 K for the sample with the lowest In content.

Cost-effective wear and oxidation resistant electrodeposited Ni-pumice coating

In the search for newer distributed phases that can be used in Ni-composite coatings, inexpensive and naturally available pumice has been identified as a potential candidate material. The composition of the pumice mineral as determined by Rietveld analysis shows the presence of corundum, quartz, mulllite, moganite and coesite phases. Pumice stone is crushed, ball-milled, dried and dispersed in a nickel sulfamate bath and Ni-pumice coatings are electrodeposited at different current densities and magnetic agitation speeds. Pumice particles are uniformly incorporated in the nickel matrix and Ni-pumice composite coatings with microhardness as high as 540 HK are obtained at the lowest applied current density. In the electrodeposited Ni-pumice coatings, the grain size of Ni increases with the applied current density. The overall intensity of texture development is slightly stronger for the Ni-pumice composite coating compared to plain Ni coating and the texture evolution is possibly not the strongest deciding factor for the enhanced properties of Ni-pumice coatings. The wear and oxidation resistances of Ni-pumice coating are commensurate with that of Ni-SiC coating electrodeposited under similar conditions. (C) 2014 Elsevier B.V. All rights reserved.

Phase transformation, improved ferroelectric and magnetic properties of (1-x) BiFeO3-xPb(Zr0.52Ti0.48)O-3 solid solutions

The authors prepared (1 - x) BiFeO3 - (x)Pb(Zr0.52Ti0.48)O-3 for x <= 0.30 by sol-gel method and investigated the material's structures, magnetic and electrical properties. Detailed Rietveld analysis of X-ray diffraction data revealed that the system retains distorted rhombohedral R3c structure for x <= 0.10 but transforms to monoclinic (Cc) structure for x > 0.10. Disappearance of some Raman modes corresponding to A1 modes and the decrease in the intensities of the remaining A1 modes with increasing x in the Raman spectra, which is a clear indication of structural modification and symmetry changes brought about by PZT doping. Enhanced magnetization with PZT doping content may be attributed to the gradual change and destruction in the spin cycloid structure of BiFeO3. The leakage current density at 3.5 kV/cm was reduced by approximately three orders of magnitude by doping PZT (x = 0.30), compared with BFO ceramics. (C) 2014 AIP Publishing LLC.

Structural refinement, optical and electrical properties of Ba1-x Sm-2x/3](Zr0.05Ti0.95)O-3 ceramics

Samarium doped barium zirconate titanate ceramics with general formula Ba1-x Sm-2x/3](Zr0.05Ti0.95)O-3 x = 0, 0.01, 0.02, and 0.03] were prepared by high energy ball milling method. X-ray diffraction patterns and micro-Raman spectroscopy confirmed that these ceramics have a single phase with a tetragonal structure. Rietveld refinement data were employed to model BaO12], SmO12], ZrO6], and TiO6] clusters in the lattice. Scanning electron microscopy shows a reduction in average grain size with the increase of Sm3+ ions into lattice. Temperature-dependent dielectric studies indicate a ferroelectric phase transition and the transition temperature decreases with an increase in Sm3+ ion content. The nature of the transition was investigated by the Curie-Weiss law and it is observed that the diffusivity increases with Sm3+ ion content. The ferroelectric hysteresis loop illustrates that the remnant polarization and coercive field increase with an increase in Sm3+ ions content. Optical properties of the ceramics were studied using ultraviolet-visible diffuse reflectance spectroscopy.

Thermoelectric properties of indium doped PbTe1-ySey alloys

Lead telluride and its alloys are well known for their thermoelectric applications. Here, a systematic study of PbTe1-ySey alloys doped with indium has been done. The powder X-Ray diffraction combined with Rietveld analysis confirmed the polycrystalline single phase nature of the samples, while microstructural analysis with scanning electron microscope results showed densification of samples and presence of micrometer sized particles. The temperature dependent transport properties showed that in these alloys, indium neither pinned the Fermi level as it does in PbTe, nor acted as a resonant dopant as in SnTe. At high temperatures, bipolar effect was observed which restricted the zT to 0.66 at 800 K for the sample with 30% Se content. (C) 2014 AIP Publishing LLC.

Co-existence of tetragonal and monoclinic phases and multiferroic properties for x <= 0.30 in the (1-x)Pb(Zr0.52Ti0.48)O-3-(x)BiFeO3 system

Compositions with x <= 0.30 in the system (1- x)Pb(Zro(0.52)Ti(0.48))O-3-(x)BiFeO3 were synthesized by sol-gel method. Rietveld analysis of X-ray diffraction data reveals tetragonal structure (P4mm) for x <= 0.05 and monoclinic (Cm) phase along with the existence of tetragonal phase for 0.10 <= x <= 0.25 and monoclinic phase for x = 0.30. Transformation of E(2TO) and E + B1 vibrational modes in the range 210-250 cm(-1) (present for x <= 0.25) into A' + A `' modes at similar to 236 cm(-1) for x = 0.30, and occurrence of new vibrational modes A' and A `' in Raman spectra for x >= 0.10 unambiguously support the presence of monoclinic phase. Occurrence of remnant polarisation and enhanced magnetization with concentration of BiFeO3 indicates superior multiferroic properties. Variation of magneto-capacitance with applied magnetic field is a strong evidence of magneto-electric multiferroic coupling in these materials. (C) 2014 Elsevier B.V. All rights reserved.

Combustion synthesized tetragonal ZrO2: Eu3+ nanophosphors: Structural and photoluminescence studies

Novel crystalline tetragonal ZrO2: Eu3+ phosphors were prepared by a facile and efficient low temperature solution combustion method at 400 +/- 10 degrees C using oxalyl dihydrazide (ODH) as fuel. The powder X-ray diffraction patterns and Rietveld confinement of as formed ZrO2: Eu3+ (1-11 mol%) confirmed the presence of body centered tetragonal phase. The crystallite size estimated from Scherrer's and W-H plots was found to be in the range of 7-17 nm. These results were in good agreement with transmission electron microscopy studies. The calculated microstrain in most of the planes indicated the presence of tensile stress along various planes of the particles. The observed space group (P4(2)/nmc) revealed the presence of cations in the 2b positions (0.75, 0.25, 0.25) and the anions in the 4d positions (0.25, 0.25, 0.45). The optical band gap energies estimated from Wood and Tauc's relation was found to be in the range 4.3-4.7 eV. Photoluminescence (PL) emission was recorded under 394 and 464 nm excitation shows an intense emission peak at 605 nm along with other emission peaks at 537, 592, 605 and 713 nm. These emission peaks were attributed to the transition of D-5(0) -> F-7(J) (J = 0, 1, 2, 3) of Eu3+ ions. The high ratio of Intensity of (D-5(0) -> F-7(2)) and (D-5(0) -> F-7(1)) infers that Eu3+ occupies sites with a low symmetry and without an inversion center. CIE color coordinates indicated the red regions which could meet the needs of illumination devices. (C) 2014 Elsevier B.V. All rights reserved.

Effect of Zirconium on the Densification of Reactively Hot-Pressed Zirconium Carbide

Densification mechanisms involved during reactive hot pressing (RHP) of zirconium carbide (ZrC) have been studied. RHP has been carried out using zirconium (Zr) and graphite (C) powders in the molar ratios 1:0.5, 1:0.67, 1:0.8, and 1:1 at 40MPa, 800 degrees C-1200 degrees C for different durations. The volume fractions of phases formed, including porosity, are determined from the measured density and from Rietveld analysis. Increased densification with an increasing nonstoichiometry in carbon has been observed. Microstructural and X-ray diffraction observations coupled with the predictions of a model based on the constitutive laws governing plastic flow of zirconium suggest that the better densification of nonstoichiometric compositions arise from the higher amount of starting Zr and also the longer duration of its availability for plastic flow during RHP. Volume shrinkage due to reaction between Zr and C and the gradual elimination of the soft metal phase limit the final density achievable. Based on these observations, a two-step RHP carried out at 800 degrees C and 1200 degrees C leads to a better densification than a single RHP at 1200 degrees C.

Phase transformation of ZrO2:Tb3+ nanophosphor: Color tunable photoluminescence and photocatalytic activities

The current study involves synthesis of a series of Tb3+ doped ZrO2 nanophosphors by solution combustion method using oxalyl dihydrazide as fuel. The as-formed ZrO2:Tb3+ nanophosphors having different concentrations of Tb3+ (1-11 mol%) were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-Visible spectroscopic techniques and the materials were subjected to photoluminescence and photocatalytic dye decolorization studies. The PXRD analysis indicates the formation of tetragonal symmetry up to 5 mol% concentration of Tb3+. Further increase in Tb3+ concentration has lead to cubic phase formation and the same was confirmed by Rietveld refinement analysis. SEM images revealed that material was highly porous in nature comprising of large voids and cracks with irregular morphology. TEM and SAED images clearly confirm the formation of high quality tetragonal nanocrystals. The emissive properties of nanophosphors were found to be dependent on Tb3+ dopant concentration. The green emission of the material was turned to white emission with the increase of Tb3+ ion concentration. The photocatalytic activities of these nanophosphors were probed for the decolorization of Congo red under UV and Sunlight irradiation. All the photocatalysts showed enhanced activity under UV light compared to Sunlight. The photocatalyst with 7 mol% Tb3+ showed enhanced activity attributed to effective separation of charge carriers due to phase transformation from tetragonal to cubic. The influence of crystallite size and PL on charge carrier trapping-recombination dynamics was investigated. The study successfully demonstrates synthesis of tetragonal and cubic ZrO2:Tb3+ green nanophosphors with superior photoluminescence and photocatalytic activities. (C) 2014 Elsevier B.V. All rights reserved.

The effect of Cu addition on the thermoelectric properties of Cu2CdGeSe4

Recently, research in copper based quaternary chalcogenide materials has focused on the study of thermoelectric properties due to the complexity in the crystal structure. In the present work, stoichiometric quaternary chalcogenide compounds Cu2+xCd1-x,GeSe4 (x = 0, 0.025, 0.05, 0.075, 0.1, 0.125) were prepared by solid state synthesis. The powder X-ray diffraction patterns of all the samples showed a tetragonal crystal structure with the space group I-42m of the main phase, whereas the samples with x = 0 and x = 0.025 revealed the presence of an orthorhombic phase in addition to the main phase as confirmed by Rietveld analysis. The elemental composition of all the samples characterized by Electron Probe Micro Analyzer showed a slight deviation from the nominal composition. The transport properties were measured in the temperature range of 300 K-723 K. The electrical conductivity of all the samples increased with increasing Cu content due to the enhancement of the hole concentration caused by the substitution of Cd (divalent) by Cu (monovalent). The positive Seebeck coefficient of all the samples in the entire temperature ranges indicates that holes are the majority carriers. The Seebeck coefficient of all the samples decreased with increasing Cu content and showed a reverse trend to the electrical conductivity. The total thermal conductivity of all the samples decreased with increasing temperature which was dominated by the lattice contribution. The maximum figure of merit ZT = 0.42 at 723 K was obtained for the compound Cu2.1Cd0.9GeSe4. (C) 2014 Elsevier Ltd. All rights reserved.

Thermoelectric properties of a Mn substituted synthetic tetrahedrite

Tetrahedrite compounds Cu12-xMnxSb4S13 (0 <= x <= 1.8) were prepared by solid state synthesis. A detailed crystal structure analysis of Cu10.6Mn1.4Sb4S13 was performed by single crystal X-ray diffraction (XRD) at 100, 200 and 300 K confirming the noncentrosymmetric structure (space group I (4) over bar 3m) of a tetrahedrite. The large atomic displacement parameter of the Cu2 atoms was described by splitting the 12e site into a partially and randomly occupied 24g site (Cu22) in addition to the regular 12e site (Cu21), suggesting a mix of dynamic and static off-plane Cu2 atom disorder. Rietveld powder XRD pattern and electron probe microanalysis revealed that all the Mn substituted samples showed a single tetrahedrite phase. The electrical resistivity increased with increasing Mn due to substitution of Mn2+ at the Cu1+ site. The positive Seebeck coefficient for all samples indicates that the dominant carriers are holes. Even though the thermal conductivity decreased as a function of increasing Mn, the thermoelectric figure of merit ZT decreased, because the decrease of the power factor is stronger than the decrease of the thermal conductivity. The maximum ZT = 0.76 at 623 K is obtained for Cu12Sb4S13. The coefficient of thermal expansion 13.5 +/- 0.1 x 10(-6) K-1 is obtained in the temperature range from 460 K to 670 K for Cu10.2Mn1.8Sb4S13. The Debye temperature, Theta(D) = 244 K for Cu10.2Mn1.8Sb4S13, was estimated from an evaluation of the elastic properties. The effective paramagnetic moment 7.45 mu(B)/f.u. for Cu10.2Mn1.8Sb4S13 is fairly consistent with a high spin 3d(5) ground state of Mn.