Design and fabrication of an automated thermal desorption gas-solid reaction system: Oxidation of ammonia and methanol over YBa2Cu3O7−δ(123) oxide systems

A fully automated, versatile Temperature Programmed Desorption (TDP), Temperature Programmed Reaction (TPR) and Evolved Gas Analysis (EGA) system has been designed and fabricated. The system consists of a micro-reactor which can be evacuated to 10−6 torr and can be heated from 30 to 750°C at a rate of 5 to 30°C per minute. The gas evolved from the reactor is analysed by a quadrupole mass spectrometer (1–300 amu). Data on each of the mass scans and the temperature at a given time are acquired by a PC/AT system to generate thermograms. The functioning of the system is exemplified by the temperature programmed desorption (TPD) of oxygen from YBa2Cu3−xCoxO7 ± δ, catalytic ammonia oxidation to NO over YBa2Cu3O7−δ and anaerobic oxidation of methanol to CO2, CO and H2O over YBa2Cu3O7−δ (Y123) and PrBa2Cu3O7−δ (Pr123) systems.

A comparative study of the interaction of CO with Cu and Cu-Zn alloy clusters

Interaction of CO with Cu clusters deposited on a ZnO(0001) crystal and on ZnO/Zn surfaces (prepared in the electron spectrometer) has been examined by UV and X-ray photoelectron spectroscopy. The interaction is stronger with the small Cu clusters deposited on ZnO/Zn surfaces. Interaction of CO is evert stronger with annealed Cu/ZnO/Zn surfaces where Cu-Zn alloy particles are present. Copyright (C) 1996 Published by Elsevier Science Ltd

Mapping of large scale 158 mu m [CII] line emission: Orion A

We present the first results of an observational programme undertaken to map the fine structure line emission of singly ionized carbon ([ CII] 157 : 7409 mum) over extended regions using a Fabry Perot spectrometer newly installed at the focal plane of a 100 cm balloon- borne far- infrared telescope. This new combination of instruments has a velocity resolution of similar to 200 km s(-1) and an angular resolution of 1.'5. During the first flight, an area of 30' x 15' in Orion A was mapped. These observations extend over a larger area than previous observations, the map is fully sampled and the spectral scanning method used enables reliable estimation of the continuum emission at frequencies adjacent to the [ CII] line. The total [ CII] line luminosity, calculated by considering up to 20% of the maximum line intensity is 0.04% of the luminosity of the far- infrared continuum. We have compared the [ CII] intensity distribution with the velocity- integrated intensity distributions of (CO)-C-13(1- 0), CI(1- 0) and CO( 3- 2) from the literature. Comparison of the [ CII], [ CI] and the radio continuum intensity distributions indicates that the largescale [ CII] emission originates mainly from the neutral gas, except at the position of M 43, where no [ CI] emission corresponding to the [ CII] emission is seen. Substantial part of the [ CII] emission from here originates from the ionized gas. The observed line intensities and ratios have been analyzed using the PDR models by Kaufman et al. ( 1999) to derive the incident UV flux and volume density at a few selected positions. The models reproduce the observations reasonably well at most positions excepting the [ CII] peak ( which coincides with the position of theta(1) Ori C). Possible reason for the failure could be the simplifying assumption of a homogeneous plane parallel slab in place of a more complicated geometry.

Microwave spectrum and structure of C(6)H(5)CCH center dot center dot center dot H(2)S complex

Rotational spectra of C(6)H(5)CCH center dot center dot center dot H(2)S, C(6)H(5)CCH center dot center dot center dot H(2)(34)S, C(6)H(5)CCH center dot center dot center dot HDS, C(6)H(5)CCH center dot center dot center dot D(2)S and C(6) H(5)CCD center dot center dot center dot H(2)S complexes have been observed using a pulsed nozzle Fourier transform microwave spectrometer. The observed spectrum is consistent with a structure in which hydrogen sulfide is located over the phenyl ring pi cloud and the distance between the centers of masses of the two monomers is 3.74 +/- 0.01 angstrom. In the complex, the H(2)S unit is shifted from the phenyl ring center towards the acetylene group. The vibrationally averaged structure has an effective Cs symmetry. Ab initio calculations were performed at MP2/aug-cc-pVDZ level of theory to locate the possible geometries of the complex. The calculations reveal the experimentally observed structure to be more stable than a coplanar arrangement of the monomers, which was observed for the C(6)H(5)CCH center dot center dot center dot H(2)O complex. Atoms in molecule theoretical analysis shows the presence of S-H center dot center dot center dot pi hydrogen bond. For the parent isotopologue, each transition frequency was found to split into two resulting from an interchange of the equivalent hydrogens of H(2)S unit in the complex. (C) 2011 Elsevier Inc. All rights reserved.

Electrochemical copolymerization of thiophene derivatives; a precursor to photovoltaic devices

This work presents an electrochemical technique for the polymerization and copolymerization of thiophene derivatives like 7,9-dithiophene-2yl-8H-cyclopenta[a]acenaphthalene-8-one and 3-hexylthiophene. The structural characterization of chemically synthesized monomers and electro-chemically synthesized polymers was carried out by nuclear magnetic resonance and Fourier transform infrared spectroscopy. Thermal characterizations indicate that copolymer has increased thermal stability than that of homopolymer. Morphological studies of the polymerized films carried out by scanning electron microscopy shows network structure of copolymer. Optical properties of the homopolymers and copolymer were studied by UV-visible spectrometer and it was observed that band gap of copolymer is less than the homopolymers. HOMO and LUMO levels, band gap values of the respective polymers were also calculated from the cyclic voltammetry technique with various scan rates. By the peak current obtained from various scan rates shows that all polymerization reactions are diffusion controlled process. Charge transfer resistances of polymers were determined using Nyquist plots. Conductivity of synthesized polymers shows higher conductivity for copolymer than homopolymers. (C) 2011 Elsevier Ltd. All rights reserved.

Complete 'melting' of charge order in hydrothermally grown Pr0.57Ca0.41Ba0.02MnO3 nanowires

Nanowires of Pr0.57Ca0.41Ba0.02MnO3 (PCBM) (diameter similar to 80-90 nm and length similar to 3.5 mu m) were synthesized by a low reaction temperature hydrothermal method. Single-phase nature of the sample was confirmed by XRD experiments. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the morphology and microstructures of the nanowires. While the bulk PCBM is known to exhibit charge order (CO) below 230 K along with a ferromagnetic transition at 110 K, SQUID measurements on the nanowires of PCBM show that the charge order is completely absent and a ferromagnetic transition occurs at 115 K. However, the magnetization in the nanowires is observed to be less compared to that in the bulk. This observation of the complete 'melting' of the charge order in the PCBM nanowires is particularly significant in view of the observation of only a weakening of the CO in the nanowires of Pr0.5Ca0.5MnO3. Electron paramagnetic resonance experiments were also carried out on the PCBM nanowires using an X-band EPR spectrometer. Characteristic differences were observed in the line width of nanowires when compared with that of the bulk.

Vapor pressure and thermodynamic properties of MgIn2O4

The vapor pressure of pure indium, and the sum of the pressures of (In) and (In2O) species over the condensed phase mixture {In} + 〈MgIn2O4〉 + 〈MgO〉, have been measured by the Knudsen effusion technique in the temperature range 1095–1350 K. The materials under study were contained in a zirconia crucible, which had a Knudsen orifice along the vertical wall. The major vapor species over the condensed phase mixture were identified as (In) and (In2O) using a mass-spectrometer. The vapor pressure of (In2O) corresponding to the reaction,View the MathML source was deduced from the experimental results;View the MathML source The standard free energy of formation of the inverse spinel 〈MgIn2O4〉 from its component oxides, is given by,View the MathML source View the MathML source The entropy of transformation of 〈In2O3〉 from the C rare-earth structure to the corundum structure is evaluated from the measured entropy of formation of (MgIn2O4) and a semi-empirical correlation for the entropy of formation of spinel phases from component oxides with rock-salt and corundum structures.

Synthesis from zinc oxalate, growth mechanism and optical properties of ZnO nano/micro structures

We report the synthesis of various morphological micro to nano structured zinc oxide crystals via simple precipitation technique. The growth mechanisms of the zinc oxide nanostructures such as snowflake, rose, platelets, porous pyramid and rectangular shapes were studied in detail under various growth conditions. The precursor powders were prepared using several zinc counter ions such as chloride, nitrate and sulphate along with oxalic acid as a precipitating agent. The precursors were decomposed by heating in air resulting in the formation of different shapes of zinc oxide crystals. Variations in ZnO nanostructural shapes were possibly due to the counter ion effect. Sulphate counter ion led to unusual rose-shape morphology. Strong ultrasonic treatment on ZnO rose shows that it was formed by irregular arrangement of micro to nano size hexagonal zinc oxide platelets. The X-ray diffraction studies confirmed the wurzite structure of all zinc oxide samples synthesized using different zinc counter ions. Functional groups of the zinc oxalate precursor and zinc oxide were identified using micro Raman studies. The blue light emission spectra of the various morphologies were recorded using luminescence spectrometer. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Cd concentration sensor based on fiber grating technology

Fiber Bragg grating (FBG) and Long Period Grating (LPG) chemical sensors are one of the most exciting developments in the field of optical fiber sensors. In this paper we have proposed a simple and effective chemical sensor based on FBG and LPG techniques for detecting the traces of cadmium (Cd) in drinking water at ppm level. The sensitiveness of these two has been compared. Also, these results have been compared with the results obtained by sophisticated spectroscopic atomic absorption and emission spectrometer instruments. For proper designing of FBG to act as a concentration sensor, the cladding region of the grating has been etched using HF solution. We have characterized the FBG concentration sensor sensitivities for different solutions of Cd concentrations varying from 0.01 ppm to 0.04 ppm and observed reflected spectrum in FBG and transmitted spectrum in LPG using Optical Spectrum Analyzer. Proper reagents have been used in the solutions for detection of the Cd species. The overall shift in wavelength is 10 nm in case of LPG and the shift of Bragg wavelength is 0.07 nm in case of FBG for 0.01-0.04 ppm concentrations. (C) 2011 Elsevier B.V. All rights reserved.

Sensitive Liquid Chromatography-Tandem Mass Spectrometry Method for the Determination of Olanzapine in Human Urine

A sensitive and selective liquid chromatographic-tandem mass spectrometric (LC-MS-MS) method was developed to determine olanzapine (OLZ) in human urine. After solid-phase extraction with SPE cartridge, the urine sample was analysed on a C-18 column (Symmetry 3.5 mu m, 50 x 4.6 mm i.d) interfaced with a triple quadrupole tandem mass spectrometer. Positive electrospray ionization was employed as the ionization source. The mobile phase consisted of ammonium acetate (pH 7.8)-acetonitrile (10:90, v/v). The method was linear over a concentration range of 1-100 ngml(-1). The lower limit of quantitation was 1 ngml(-1). The intra-day and inter-day relative standard deviation across three validation runs over the entire concentration range was < 11.5 %. The accuracy determined at three concentrations (8.0, 50.0 and 85.0 ngml(-1) OLZ) was within +/- 1.21 % in terms of relative errors.

In vitro bioactivity and cytocompatibility properties of spark plasma sintered HA-Ti composites

The present study reports the results of the detailed in vitro bioactivity and cytocompatibility properties of the hydroxyapatite (HA) and the HA-titanium (HA-Ti) composite with varying amount of Ti (5, 10, and 20 wt %), densified using spark plasma sintering process (SPS). Using this technique and tailoring suitable processing parameters, it has been possible to retain both HA and Ti in the sintered ceramics. Importantly, the uniquely designed SPS processing with suitably chosen parameters enables in achieving better mechanical properties, such as higher indentation fracture toughness (similar to 1.5 MPa m1/2) in HA-Ti composites compared with HA. X-ray diffraction and scanning electron microscopic (SEM) observations reveal good bioactivity of the HA-Ti composites with the formation of thick, flaky, and porous apatite layer when immersed in simulated body fluid at 37 degrees C and pH of 7.4. Atomic absorption spectroscopic analysis of the simulated body fluid solution reveals dynamic changes in Ca+2 ion concentration with more dissolution of Ca+2 ion from the HA-20Ti composite. However, the measurements with inductively coupled plasma spectrometer do not record dissolution of Ti+4 ions. Transmission electron microscopic analysis indicates weak crystalline nature of the apatite and confirms the formation of fine-scale apatite crystals. MTT assay, fluorescence, and SEM study demonstrate good cell viability and cell adhesion/proliferation of the Saos -2 cells, cultured on the developed composites under standard culture condition, and the difference in cell viability has been discussed in reference to substrate composition and roughness. Overall, HA-Ti composites exhibit comparable and even better in vitro bioactivity and cytocompatibility properties than HA. (c) 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2013.

Feasibility of laser-induced breakdown spectroscopy for the study of the temporal distribution of trace elements trapped in snow collected from greater himalayan range

The potential merit of laser-induced breakdown spectroscopy (LIBS) has been demonstrated for detection and quantification of trace pollutants trapped in snow/ice samples. In this technique, a high-power pulsed laser beam from Nd:YAG Laser (Model no. Surelite III-10, Continuum, Santa Clara, CA, USA) is focused on the surface of the target to generate plasma. The characteristic emissions from laser-generated plasma are collected and recorded by a fiber-coupled LIBS 2000+ (Ocean Optics, Santa Clara, CA, USA) spectrometer. The fingerprint of the constituents present in the sample is obtained by analyzing the spectral lines by using OOI LIBS software. Reliable detection of several elements like Zn, Al, Mg, Fe, Ca, C, N, H, and O in snow/ice samples collected from different locations (elevation) of Manali and several snow samples collected from the Greater Himalayan region (from a cold lab in Manali, India) in different months has been demonstrated. The calibration curve approach has been adopted for the quantitative analysis of these elements like Zn, Al, Fe, and Mg. Our results clearly demonstrate that the level of contamination is higher in those samples that were collected in the month of January in comparison to those collected in February and March.

An experimental set-up for carbon isotopic analysis of atmospheric CO2 and an example of ecosystem response during solar eclipse 2010

We present here, an experimental set-up developed for the first time in India for the determination of mixing ratio and carbon isotopic ratio of air-CO2. The set-up includes traps for collection and extraction of CO2 from air samples using cryogenic procedures, followed by the measurement of CO2 mixing ratio using an MKS Baratron gauge and analysis of isotopic ratios using the dual inlet peripheral of a high sensitivity isotope ratio mass spectrometer (IRMS) MAT 253. The internal reproducibility (precision) for the PC measurement is established based on repeat analyses of CO2 +/- 0.03 parts per thousand. The set-up is calibrated with international carbonate and air-CO2 standards. An in-house air-CO2 mixture, `OASIS AIRMIX' is prepared mixing CO2 from a high purity cylinder with O-2 and N-2 and an aliquot of this mixture is routinely analyzed together with the air samples. The external reproducibility for the measurement of the CO2 mixing ratio and carbon isotopic ratios are +/- 7 (n = 169) mu mol.mol(-1) and +/- 0.05 (n = 169) parts per thousand based on the mean of the difference between two aliquots of reference air mixture analyzed during daily operation carried out during November 2009-December 2011. The correction due to the isobaric interference of N2O on air-CO2 samples is determined separately by analyzing mixture of CO2 (of known isotopic composition) and N2O in varying proportions. A +0.2 parts per thousand correction in the delta C-13 value for a N2O concentration of 329 ppb is determined. As an application, we present results from an experiment conducted during solar eclipse of 2010. The isotopic ratio in CO2 and the carbon dioxide mixing ratio in the air samples collected during the event are different from neighbouring samples, suggesting the role of atmospheric inversion in trapping the emitted CO2 from the urban atmosphere during the eclipse.

SARAS: a precision system for measurement of the cosmic radio background and signatures from the epoch of reionization

SARAS is a correlation spectrometer purpose designed for precision measurements of the cosmic radio background and faint features in the sky spectrum at long wavelengths that arise from redshifted 21-cm from gas in the reionization epoch. SARAS operates in the octave band 87.5-175 MHz. We present herein the system design arguing for a complex correlation spectrometer concept. The SARAS design concept provides a differential measurement between the antenna temperature and that of an internal reference termination, with measurements in switched system states allowing for cancellation of additive contaminants from a large part of the signal flow path including the digital spectrometer. A switched noise injection scheme provides absolute spectral calibration. Additionally, we argue for an electrically small frequency-independent antenna over an absorber ground. Various critical design features that aid in avoidance of systematics and in providing calibration products for the parametrization of other unavoidable systematics are described and the rationale discussed. The signal flow and processing is analyzed and the response to noise temperatures of the antenna, reference termination and amplifiers is computed. Multi-path propagation arising from internal reflections are considered in the analysis, which includes a harmonic series of internal reflections. We opine that the SARAS design concept is advantageous for precision measurement of the absolute cosmic radio background spectrum; therefore, the design features and analysis methods presented here are expected to serve as a basis for implementations tailored to measurements of a multiplicity of features in the background sky at long wavelengths, which may arise from events in the dark ages and subsequent reionization era.

Variable field ion traps

This paper presents a technique to vary the electric field within a cylindrical ion trap (CIT) mass spectrometer while it is in operation. In this technique, the electrodes of the CIT are split into number of mini-electrodes and different voltages are applied to these split-electrodes to achieve the desired field. In our study we have investigated two geometries of the split-electrode CIT. In the first, we retain the flat endcap electrodes of the CIT but split the ring electrode into five mini-rings. In the second configuration, we split the ring electrode of the CIT into three mini-rings and also divide the endcaps into two mini-discs. By applying different potentials to the mini-rings and mini-discs of these geometries we have shown that the field within the trap can be optimized to desired values. In our study, two different types of fields were targeted. In the first, potentials were adjusted to obtain a linear electric field and, in the second, a controlled higher order even multipole field was obtained by adjusting the potential. We have shown that the different potentials required can be derived from a single RF generator by connecting appropriate capacitor terminations to split electrodes. The field within the trap can be modified by changing the values of the external capacitors. (C) 2013 Elsevier B.V. All rights reserved.