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.

Observation of Combined Effect of Temperature and Pressure on Cubic to Hexagonal Phase Transformation in ZnS at the Nanoscale

The temperature of allotropic phase transformation in ZnS (cubic to wurtzite) changes with pressure and particle size. In this paper we have explored the interrelation among these through a detailed study of ZnS powders obtained by a temperature-controlled high energy milling process. By employing the combined effect of temperature and pressure in an indigenously built cryomill, we have demonstrated a large-scale, low-temperature synthesis of wurtzite ZnS nanoparticles. The synthesized products have been characterized for their phase and microstructure by the use of X-ray diffraction and transmission electron microscopic techniques. Further, it has been demonstrated that the synthesized materials exhibit photoluminescence emissions in the UV-visible region with an unusual doublet pattern due to the presence of both cubic and hexagonal wurtzite domains in the same particles. By further fine-tuning the processing conditions, it may be possible to achieve controlled defect related photoluminescence emissions from the ZnS nanoparticles.

First and second law thermodynamic analysis of air and oxy-steam biomass gasification

Gasification is an energy transformation process in which solid fuel undergoes thermochemical conversion to produce gaseous fuel, and the two most important criteria involved in such process to evaluate the performance, economics and sustainability of the technology are: the total available energy (exergy) and the energy conserved (energy efficiency). Current study focuses on the energy and exergy analysis of the oxy-steam gasification and comparing with air gasification to optimize the H-2 yield, efficiency and syngas energy density. Casuarina wood is used as a fuel, and mixture of oxygen and steam in different proportion and amount is used as a gasifying media. The results are analysed with respect to varying equivalence ratio and steam to biomass ratio (SBR). Elemental mass balance technique is employed to ensure the validity of results. First and second law thermodynamic analysis is used towards time evaluation of energy and exergy analysis. Different component of energy input and output has been studied carefully to understand the influence of varying SBR on the availability of energy and irreversibility in the system to minimize the losses with change in input parameters for optimum performance. The energy and exergy losses (irreversibility) for oxy-steam gasification system are compared with the results of air gasification, and losses are found to be lower in oxy-steam thermal conversion; which has been argued and reasoned due to the presence of N-2 in the air-gasification. The maximum exergy efficiency of 85% with energy efficiency of 82% is achieved at SBR of 0.75 on the molar basis. It has been observed that increase in SBR results in lower exergy and energy efficiency, and it is argued to be due to the high energy input in steam generation and subsequent losses in the form of physical exergy of steam in the product gas, which alone accounts for over 18% in exergy input and 8.5% in exergy of product gas at SBR of 2.7. Carbon boundary point (CBP), is identified at the SBR of 1.5, and water gas shift (WGS) reaction plays a crucial role in H-2 enrichment after carbon boundary point (CBP) is reached. Effects of SBR and CBP on the H-2/CO ratio is analysed and discussed from the perspective of energy as well as the reaction chemistry. Energy density of syngas and energy efficiency is favoured at lower SBR but higher SBR favours H-2 rich gas at the expense of efficiency. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

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.

Copper-Catalyzed Direct Transformation of Secondary Allylic and Benzylic Alcohols into Azides and Amides: An Efficient Utility of Azide as a Nitrogen Source

A mild and convenient method for the synthesis of amides has been explored by using secondary alcohols, Cu(ClO4)(2)6H(2)O as a catalyst, and trimethylsilyl azide (TMSN3) as a nitrogen source in the presence of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) at ambient temperature. This method has been successfully adapted to the preparation of azides directly from their corresponding alcohols and offers excellent chemoselectivity in the formation of -halo azides and the azidation of allylic alcohols in the presence of a benzyl alcohol moiety. In addition, this strategy provides an opportunity to synthesize azides that can serve as precursors to -amino acids.

Rapidly solidified nonequilibrium microstructure and phase transformation of laser-synthesized iron-based alloy coating

The rapidly solidified microstructural and compositional features, the precipitation and transformation of carbides during tempering, and the impact wear resistance of an iron-based alloy coating prepared by laser cladding are investigated. The clad coating alloy, a powder mixture of Fe, Cr, W, Ni, and C with a weight ratio of 10:5:1.1.1, is processed using a continuous wave CO, laser. Microstructural studies demonstrate that the coating possesses the hypoeutectic microstructure comprising the primary dendritic gamma-austenite and interdendritic eutectic consisting of gamma-austenite and M7C3 carbides. gamma-Austenite is a non-equilibrium phase with an extended solid solution of alloying elements. During high temperature tempering at 963 K for 1 h, the precipitation of M23C6, MC and M2C carbides in austenite and in situ carbide transformation of M7C3 to M23C6 and M7C3 to M6C respectively are observed. In addition, the microstructure of the laser-clad coating reveals an evident secondary hardening and a superior impact wear resistance.

A generalized treatment of the order-disorder transformation in alloys and its effects on their magnetic properties

A theory of the order-disorder transformation is developed in complete generality. The general theory is used to calculate long range order parameters, short range order parameters, energy, and phase diagrams for a face centered cubic binary alloy. The theoretical results are compared to the experimental determination of the copper-gold system, Values for the two adjustable parameters are obtained.

An explanation for the behavior of magnetic alloys is developed, Curie temperatures and magnetic moments of the first transition series elements and their alloys in both the ordered and disordered states are predicted. Experimental agreement is excellent in most cases. It is predicted that the state of order can effect the magnetic properties of an alloy to a considerable extent in alloys such as Ni₃Mn. The values of the adjustable parameter used to fix the level of the Curie temperature, and the adjustable parameter that expresses the effect of ordering on the Curie temperature are obtained.

A Biogeographic assessment off North/Central California: In support of the National Marine Sanctuaries of Cordell Bank, Gulf of the Farallones and Monterey Bay. Phase II - Environmental setting and update to marine birds and animals

NOAA’s National Centers for Coastal Ocean Science (NCCOS) conducts and supports research, monitoring, assessments, and technical assistance to meet NOAA’s coastal stewardship and management responsibilities. In 2001 the Biogeography Branch of NCCOS partnered with NOAA’s National Marine Sanctuary Program (NMSP) to conduct biogeographic assessments to support the management plan updates for the sanctuaries. The first biogeographic assessment conducted in this partnership focused on three sanctuaries off north/ central California: Cordell Bank, Gulf of the Farallones and Monterey Bay. Phase I of this assessment was conducted from 2001 to 2004, with the primary goal to identify and gather the best available data and information to characterize and identify important biological areas and time periods within the study area. The study area encompasses the three sanctuaries and extends along the coastal ocean off California from Pt. Arena to Pt. Sal (35°-39°N). This partnership project was lead by the NCCOS Biogeography Branch, but included over 90 contributors and 25 collaborating institutions. Phase I results include: 1) a report on the overall assessment that includes hundreds of maps, tables and analyses; 2) an ecological linkage report on the marine and estuarine ecosystems along the coast of north/central California, and 3) related geographic information system (GIS) data and other summary data files, which are available for viewing and download in several formats at the following website: http://ccma.nos.noaa.gov/products/biogeography/canms_cd/welcome.html Phase II (this report) was initiated in the Fall of 2004 to complete the analyses of marine mammals and update the marine bird colony information. Phase II resulted in significant updates to the bird and mammal chapters, as well as adding an environmental settings chapter, which contains new and existing data and maps on the study area. Specifically, the following Phase II topics and items were either revised or developed new for Phase II: •environmental, ecological settings – new maps on marine physiographic features, sea surface temperature and fronts, chlorophyll and productivity •all bird colony or roost maps, including a summary of marine bird colonies •updated at-sea data CDAS data set (1980-2003) •all mammal maps and descriptions •new overall density maps for eight mammal species •new summary pinniped rookery/haulout map •new maps on at-sea richness for cetaceans and pinnipeds •most text in the mammal chapter •new summary tables for mammals on population status and spatial and temporal patterns