Ce0.67Cr0.33O2.11: A New Low-Temperature O-2 Evolution Material and H-2 Generation Catalyst by Thermochemical Splitting of Water

Ce0.67Cr0.33O2.11 was synthesized by hydrothermal method using diethylenetriamine as complexing agent (Chem. Mater. 2008, 20, 7268). Ce0.67Cr0.33O2.11 being the only compound likes UO2+delta to have excess oxygen, it releases a large proportion of its lattice oxygen (0.167 M [O]/mole of compound) at relatively low temperature (465 degrees C) directly and it has been utilized for generation of H-2 by thermo-splitting of water. An almost stoichiometric amount of H-2 (0.152 M/Mole of compound) is generated at much lower temperature (65 degrees C). There is an almost comparable amount of oxygen release and hydrogen generation over this material at very low temperature comparedto other CeO2-MOx (Mn, Fe, Cu, and Ni) mixed-oxide solid solutions (O-2 evolution >= 1300 degrees C and H-2 generation at 1000 degrees C). The reversible nature of oxygen release and intake of this material is attributed to its fluorite Structure and coupling between the Ce4+/Ce3+ and Cr4+/6+/Cr3+ redox couples. Compound shows reversible oxygen release and intake by H2O absorption and subsequent hydrogen release to gain parent structure and hence this material can be utilized for generation of H-2 at very low temperature by thermo-chemical splitting of water.

Microsphere Bouquets of Bismuth Telluride Nanoplates: Room-Temperature Synthesis and Thermoelectric Properties

We report the synthesis and properties of sphere-shaped microscale aggregates of bismuth telluride nanoplates. We obtain porous microspheres by reducing bismuth chloride and orthotelluric acid with hydrazine in the presence of thioglycolic acid-which serves as the shape-and size-directing agent-followed by room-temperature aging-which promotes nanoplate aggregation. Thin film assemblies of the nanoplate microspheres exhibit n-type behavior due to sulfur doping and a Seebeck coefficient higher than that reported for assemblies of chalcogenide nanostructures. Adaptation of our scalable approach to synthesize and hierarchically assemble nanostructures with controlled doping could be attractive for tailoring novel thermoelectric materials for applications in high-efficiency refrigeration and harvesting electricity from heat.

Apparent shortening of the Csp(3)-Csp(3) bond analysed via a variable-temperature X-ray diffraction study in racemic 1,1 '-binaphthalene-2,2 '-diyl diethyl bis(carbonate)

Crystal structure determination at room temperature [292 (2) K] of racemic 1,1'-binaphthalene-2,2'-diyl diethyl bis(carbonate), C26H22O6, showed that one of the terminal carbon-carbon bond lengths is very short [Csp(3)-Csp(3) = 1.327 (6) angstrom]. The reason for such a short bond length has been analysed by collecting data sets on the same crystal at 393, 150 and 90 K. The values of the corrected bond lengths clearly suggest that the shortening is mainly due to positional disorder at two sites, with minor perturbations arising as a result of thermal vibrations. The positional disorder has been resolved in the analysis of the 90 K data following the changes in the unit-cell parameters for the data sets at 150 and 90 K, which appear to be an artifact of a near centre of symmetry relationship between the two independent molecules in the space group P (1) over bar at these temperatures. Indeed, the unit cell at low temperature (150 and 90 K) is a supercell of the room-temperature unit cell.

Electrochemical properties and intermediate-temperature fuel cell performance of dense yttrium-doped barium zirconate with calcium addition

Although BaZr 0.8Y 0.2O 3-δ(BZY) possesses large bulk proton conductivity and excellent chemical stability, its poor sinterability and grain boundaries block proton conduction. In this work, the effect of Ca as a co-dopant and as a sintering aid (as CaO), on the sinterability, proton conductivity, and fuel cell performance of BZY was investigated. The addition of 4 mol% CaO significantly improved the BZY sinterability: BZY pellets with densities of 92.7% and 97.5% with respect to the theoretical density were obtained after sintering at 1500°C and 1600°C, respectively. The improved BZY sinterability by CaO addition resulted also in a large proton conductivity; at 600°C, the total conductivity of BZY-CaO was 2.14 × 10 -3 S/cm, in wet Ar. Anode-supported fuel cells with 25 μm-thick BZY-CaO electrolyte membranes were fabricated by a dual-layer co-firing technique. The peak power density of the fuel cell with a BZY-Ni/BZY-4CaO/BZY-LSCF (La 0.6Sr 0.4Fe 0.8Co 0.2O 3-δ) configuration was 141 mW/cm 2 at 700°C, several times larger than the reported values of BZY electrolyte membrane fuel cells sintered with the addition of CuO or ZnO, demonstrating promising features for practical fuel cell applications.

Low-temperature synthesis and sintering of γ-Y2Si2O7

In this article, a novel pressureless solid-liquid reaction method is presented for preparation of yttrium disilicate (γ-Y2Si2O7). Single-phase γ-Y2Si2O7 powder was synthesized by calcination of SiO2 and Y2O3 powders with the addition of LiYO2 at 1400 °C for 4 h. The addition of LiYO2 significantly decreased the synthesis temperature, shortened the calcination time, and enhanced the stability of γ-Y2Si2O7. The sintering of these powders in air and O2 was studied by means of thermal mechanical analyzer. It is shown that the γ-Y2Si2O7 sintered in oxygen had a faster densification rate and a higher density than that sintered in air. Furthermore, single-phase γ-Y2Si2O7 with a density of 4.0 g/cm3 (99% of the theoretical density) was obtained by pressureless sintering at 1400 °C for 2 h in oxygen. Microstructures of the sintered samples are studied by scanning electron microscope.

Implantation Induced Hardening of Nanocrystalline Titanium Thin Films

Formation of nanocrystalline TiN at low temperatures was demonstrated by combining Pulsed Laser Deposition (PLD) and ion implantation techniques. The Ti films of nominal thickness similar to 250 nm were deposited at a substrate temperature of 200 degrees C by ablating a high pure titanium target in UHV conditions using a nanosecond pulsed Nd:YAG laser operating at 1064 nm. These films were implanted with 100 keV N+ ions with fluence ranging from 1.0 x 10(16) ions/cm(2) to 1.0 x 10(17) ions/cm(2). The structural, compositional and morphological evolutions were tracked using Transmission Electron Microscopy (TEM), Secondary Ion Mass Spectrometry (SIMS) and Atomic Force Microscopy (AFM), respectively. TEM analysis revealed that the as-deposited titanium film is an fcc phase. With increasing ion fluence, its structure becomes amorphous phase before precipitation of nanocrystalline fcc TiN phase. Compositional depth profiles obtained from SIMS have shown the extent of nitrogen concentration gradient in the implantation zone. Both as-deposited and ion implanted films showed much higher hardness as compared to the bulk titanium. AFM studies revealed a gradual increase in surface roughness leading to surface patterning with increase in ion fluence.

Constitutive equation for elevated temperature flow behavior of plain carbon steels using dimensional analysis

Dimensional analysis using π-theorem is applied to the variables associated with plastic deformation. The dimensionless groups thus obtained are then related and rewritten to obtain the constitutive equation. The constants in the constitutive equation are obtained using published flow stress data for carbon steels. The validity of the constitutive equation is tested for steels with up to 1.54 wt%C at temperatures: 850–1200 °C and strain rates: 6 × 10−6–2 × 10−2 s−1. The calculated flow stress agrees favorably with experimental data.

Expression of hyoscyamine 6 beta-hydroxylase in the root pericycle cells and accumulation of its product scopolamine in leaf and stem tissues of Datura metel L.

Hyoscyamine 60-hydroxylase (H6H: EC 1.14.11.11), a key enzyme at the terminal step of tropane alkaloid biosynthesis, converts hyoscyamine to scopolamine. The accumulation of scopolamine in different organs, in particular the aerial parts for storage, is subject to the expression of hyoscyamine 6-phydroxylase as well as its transport from the site of synthesis. To understand the molecular basis of this regulation, we have analyzed, in parallel, the relative levels of hyoscyamine and scopolamine, and the accumulation of H6H (both protein and transcript) in leaves, stems and roots of D. metel. The root, stem and leaf tissues all contain about 0.51-0.65 mg g(-1) dry weight of scopolamine. Hyoscyamine content was extremely low in leaf and stem tissues and was about 0.28 mg g(-1) dry weight in the root tissue. H6H protein and its transcript were found only in roots but not in the aerial parts viz. stems and leaves. The immunolocalization studies performed on leaf, stem, root as well as hairy root tissues showed that H6H was present only in the pericycle cells of young lateral and hairy roots. These studies suggest that the conversion of hyoscyamine to scopolamine takes place in the root pericycle cells, and the alkaloid biosynthesized in the roots gets translocated to the aerial parts in D. metel. (C) 2009 Elsevier Ireland Ltd. All rights reserved.

Low-temperature Er3+ emission in Ge-S-Ga glasses excited by host absorption

The photoluminescence (PL) of a series of (GeS2)(80)(Ga2S3)(20) glasses doped with different amounts of Er (0.17, 0.35, 0.52, 1.05 and 1.39 at.%) at 77 and 4.2 K has been studied. The influence of the temperature on the emission cross-section of the PL bands at -> 1540, 980 and 820 nm under host excitation has been defined. A quenching effect of the host photoluminescence has been established from the compositional dependence of the PL intensity. It has been found that the present Er3+-doped Ge-S-Ga glasses posses PL lifetime values about 3.25 ms. (C) 2007 Elsevier B.V. All rights reserved.

Temperature monitoring of nonanaesthetised patients in a cardiac catheterisation laboratory

Aim and objectives To identify the prevalence that temperature reduced by more than 1°C from pre to post-procedure in a sample of non-anaesthetised patients undergoing procedures in a cardiac catheterisation laboratory. Background Advances in medical technology are minimising the invasiveness of diagnostic tests and treatments for disease, which is correspondingly increasing the number of medical procedures performed without sedation or anaesthesia. Procedural areas in which medical procedures are performed without anaesthesia are typically kept at a cool temperature for staff comfort. As such, there is a need to inform nursing practices in regard to the thermal management of non-anaesthetised patients undergoing procedures in surgical or procedural environments. Design Single-site observational study Methods Patients were included if they had undergone an elective procedure without sedation or anaesthesia in a cardiac catheterisation laboratory. Ambient room temperature was maintained between 18°C and 20°C. Passive warming with heated cotton blankets was applied. Nurses measured body temperature and thermal comfort before and after 342 procedures. Results Mean change in temperature was -0.08°C (Standard deviation 0.43). The reduction in temperature was more than 1°C after 11 procedures (3.2%). One patient whose temperature had reduced more than 1°C after their procedure reported thermal discomfort. A total of 12 patients were observed to be shivering post-procedure (3.6%). No demographic or clinical characteristics were associated with reduction in temperature of more than 1°C from pre to post-procedure. Conclusions Significant reduction in body temperature was rare in our sample of non-anaesthetised patients. Relevance to clinical practice Similar results would likely be found in other procedural contexts during procedures conducted in settings with comparable room temperatures where passive warming can also be applied with limited skin exposure.

Temperature-dependent infrared reflectivity studies of multiferroic TbMnO3: Evidence for spin-phonon coupling

We have measured near normal incidence far-infrared (FIR) reflectivity spectra of a single crystal of TbMnO3 from 10 K to 300 K in the spectral range of 50 cm(-1)-700 cm(-1). Fifteen transverse optic (TO) and longitudinal optic (LO) modes are identified in the imaginary part of the dielectric function epsilon(2)(omega) and energy loss function Im(-1/epsilon(omega)), respectively. Some of the observed phonon modes show anomalous softening below the magnetic transition temperature T-N (similar to 46 K). We attribute this anomalous softening to the spin-phonon coupling caused by phonon modulation of the superexchange integral between the Mn3+ spins. The effective charge of oxygen (Z(O)) calculated using the measured LO-TO splitting increases below TN.

Possible high-temperature superconducting state with a d plus id pairing symmetry in doped graphene

Motivated by a suggestion in our earlier work [G. Baskaran, Phys. Rev. B 65, 212505 (2002)], we study electron correlation driven superconductivity in doped graphene where on-site correlations are believed to be of intermediate strength. Using an extensive variational Monte Carlo study of the repulsive Hubbard model and a correlated ground state wave function, we show that doped graphene supports a superconducting ground state with a d+id pairing symmetry. We estimate superconductivity reaching room temperatures at an optimal doping of about 15%-20%. Our work suggests that correlations can stabilize superconductivity even in systems with intermediate coupling.

Highly biocompatible and water-dispersible, amine functionalized magnetite nanoparticles, prepared by a low temperature, air-assisted polyol process: a new platform for bio-separation and diagnostics

A low temperature polyol process, based on glycolaldehyde mediated partial reduction of FeCl3 center dot 6H(2)O at 120 degrees C in the presence of sodium acetate as an alkali source and 2,2'-(ethylenedioxy)-bis-(ethylamine) as an electrostatic stabilizer has been used for the gram-scale preparation of biocompatible, water-dispersible, amine functionalized magnetite nanoparticles (MNPs) with an average diameter of 6 +/- 0.75 nm. With a reasonably high magnetization (37.8 e.m.u.) and amine groups on the outer surface of the nanoparticles, we demonstrated the magnetic separation and concentration implications of these ultrasmall particles in immunoassay. MRI studies indicated that these nanoparticles had the desired relaxivity for T-2 contrast enhancement in vivo. In vitro biocompatibility, cell uptake and MR imaging studies established that these nanoparticles were safe in clinical dosages and by virtue of their ultrasmall sizes and positively charged surfaces could be easily internalized by cancer cells. All these positive attributes make these functional nanoparticles a promising platform for further in vitro and in vivo evaluations.

Low-frequency resistance fluctuations in metal films under current stressing at low temperature (T<0.3Tmelting)

In this paper, we report a systematic study of low frequency 1∕fα resistance fluctuation in thin metal films (Ag on Si) at different stages of damage process when the film is subjected to high current stressing. The resistance fluctuation (noise) measurement was carried out in situ using a small ac bias that has been mixed with the dc stressing current. The experiment has been carried out as a function of temperature in the range of 150–350 K. The experiment establishes that the current stressed film, as it undergoes damage due to various migration forces, develops an additional low-frequency noise spectral power that does not have the usual 1∕f spectral shape. The magnitude of extra term has an activated temperature dependence (activation energy of ≈0.1 eV) and has a 1∕f1.5 spectral dependence. The activation energy is the same as seen from the temperature dependence of the lifetime of the film. The extra 1∕f1.5 spectral power changes the spectral shape of the noise power as the damage process progress. The extra term likely arising from diffusion starts in the early stage of the migration process during current stressing and is noticeable much before any change can be detected in simultaneous resistance measurements. The experiment carried out over a large temperature range establish a strong correlation between the evolution of the migration process in a current stressed film and the low-frequency noise component that is not a 1∕f noise.

Low-Temperature Processing of ZrB2-ZrC Composites by Reactive Hot Pressing

Dense ZrB2-ZrC and ZrB2-ZrC x∼0.67 composites have been produced by reactive hot pressing (RHP) of stoichiometric and nonstoichiometric mixtures of Zr and B4C powders at 40 MPa and temperatures up to 1600 °C for 30 minutes. The role of Ni addition on reaction kinetics and densification of the composites has been studied. Composites of ∼97 pct relative density (RD) have been produced with the stoichiometric mixture at 1600 °C, while the composite with ∼99 pct RD has been obtained with excess Zr at 1200 °C, suggesting the formation of carbon deficient ZrC x that significantly aids densification by plastic flow and vacancy diffusion mechanism. Stoichiometric and nonstoichiometric composites have a hardness of ∼20 GPa. The grain sizes of ZrB2 and ZrC x∼0.67 are ∼0.6 and 0.4 μm, respectively, which are finer than those reported in the literature.