Temperature- and pressure-dependent study of Cl-35 NQR frequency and spin lattice relaxation time in 2,3-dichloroanisole

The temperature and pressure dependence of Cl-35 NQR frequency and spin lattice relaxation time (T-1) were investigated in 2,3-dichloroanisole. Two NQR signals were observed throughout the temperature and pressure range studied. T-1 were measured in the temperature range from 77 to 300 K and from atmospheric pressure to 5 kbar. Relaxation was found to be due to the torsional motion of the molecule and also reorientation f motion of the CH3 group. T-1 versus temperature data were analyzed on the basis of Woessner and Gutowsky model, and the activation energy for the reorientation of the CH3 group was estimated. The temperature dependence of the average torsional lifetimes of the molecules and the transition probabilities were also obtained. NQR frequency shows a nonlinear behavior with pressure, indicating both dynamic and static effects of pressure. The pressure coefficients were observed to be positive for both the lines. A thermodynamic analysis of the data was carried out to determine the constant volume temperature coefficients of the NQR frequency. The variation of spin lattice time with pressure was very small, showing that the relaxation is mainly due to the torsional motions of the molecules. Copyright (C) 2010 John Wiley & Sons, Ltd.

On-board correction of systematic error of Earth sensors

Infrared Earth sensors are used in spacecraft for attitude sensing. Their accuracy is limited by systematic and random errors. Dominant sources of systematic errors are analyzed for a typical scanning infrared Earth sensor used in a remote-sensing satellite in a 900-km sun-synchronous orbit. The errors considered arise from 1) seasonable variation of infrared radiation, 2) oblate shape of the Earth, 3) ambient temperature of sensors, 4) changes in spin/scan period, and 5) misalignment of the axis of the sensors. Simple relations are derived using least-squares curve fitting for onboard correction of these errors. With these, it is possible to improve the accuracy of attitude determination by eight fold and achieve performance comparable to ground-based post-facto attitude computation.

High-pressure NMR investigations of the protonic conductor (NH4)4Fe(CN)6.1.5H2O

The effect of high hydrostatic pressure up to 1.5 GPa on ionic motion in (NH4)4Fe(CN)6.1.5H2O has been studied by wide-line 1H NMR experiments performed in the temperature range from room temperature to 77 K. The experiments at room temperature have shown a large increase in the second moment at 0.45 GPa as a result of a pressure-induced phase transition. The temperature dependence study up to 0.425 GPa has shown a gradual increase in the values of activation energy and attempt frequency with increase in pressure. The activation volume for motion at 300 K has been estimated to be 6% of molar volume. Vacancy-assisted ionic jumps are concluded to be the mode of charge transport. Second moments estimated at 77 K show evidence for tunnelling reorientation of at least one of the two NH4+ groups in the compound.

A series of metallic oxides of the formula La3LnBaCu5O13+δ (Ln = rare earth or Y)

Oxides of the formula La3LnBaCu5O13+δ (Ln = Nd, Sm, Gd, Dy, or Y) exhibiting metallic resistivity have been prepared and characterized. In the case of yttrium, a composition close to La2Y2BaCu5O13+δ, which is also metallic, could be prepared.

Pressure induced incommensurate to commensurate transition in K3Cu8S6

To study the effect of hydrostatic pressure on the incommensurate lattice modulation at 153 K in K3Cu8S6, electrical resistivity measurements are done at 1.0 GPa, 1.5 GPa and 2.2 GPa. The sharp increase in resistance at 2.2 GPa is attributed to the incommensurate to commensurate transition. This is further confirmed by the non-linear I–V characteristics at 2.2 GPa showing the driven motion of the commensurate charge density wave in the presence of an external electric field.

Towards a green synthesis of LAB's: Effect of rare earth metal ions on the benzene alkylation with 1-dodecene over NaFAU-Y zeolites

Chemically modified microporous materials can be prepared as robust catalysts suitable for application in vapor phase processes such as Friedel-Crafts alkylation. In the present paper we have investigated the use of rare earth metal (Ce3+, La3+, RE3+, and Sm3+) exchanged Na-Y zeolites as catalysts for the alkylation of benzene with long chain linear 1-olefin; 1-dodecene. Thermodesorption studies of 2,6-dimethylpyridine adsorbed catalysts (in the temperature range 573 to 873 K) show that the rare earth zeolites are highly Bronsted acidic in nature. A perfect correlation between catalyst selectivity towards the desired product (2-phenyldodecane) and Bronsted acid sites amount has been observed. (c) 2006 Springer Science + Business Media, Inc.

High-pressure studies on Ge-Te glasses. Evidence for a critical composition in IV-VI chalcogenide glassy systems

The electrical resistivity of bulk GexTe100-x glasses has been measured as a function of temperature and pressure. Under high pressure, all the glasses were found to undergo sharp discontinuous transitions from glassy semiconductors to crystalline metal. Several of the observed properties such as the transition pressure, conductivity activation energy and pre-exponential factor, exhibit anomalous trends at a composition x = 20. These results suggest that the x = 20 composition in the Ge-Te system should possess salient structural features. A model based on the unusual stability of structural units is proposed for explaining the anomaly at 20 at.% Ge concentration.

NMR study of ammonium halides under high pressure

Wide-line c.w. proton resonance investigations have been carried out on the ammonium halides, namely, ammonium chloride, ammonium bromide and ammonium iodide in the temperature range between 77 and 300 K and in the pressure range between 1 bar and 14 kbar. It has been found that the narrow iodide spectrum at 77 K broadens under the application of hydrostatic pressure. The barrier height for the ammonium ion motion in ammonium iodide under pressure has been estimated by carrying out a temperature variation study. The rotational potential for the motion of ammonium ion in ammonium iodide at 1 bar and 14 kbar has been calculated using earlier theoretical models and compared with values calculated for ammonium chloride and bromide. The barrier height in the case of ammonium iodide under pressure is found to be of the same order of magnitude as the value obtained in the case of ammonium bromide at atmospheric pressure indicating that the high pressure phase of ammonium iodide is likely to have the same structure as the low temperature ordered CsCl phase found in the case of the chloride and the bromide. The increase in the potential barrier height in the case of ammonium iodide under pressure indicates that the reorientational motion executed by the ammonium ions is inhibited by the application of pressure. This is also confirmed by the broadening of the spectral line at 77 K under the application of pressure.

Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO2 from First Principles Calculation

Oxygen storage/release (OSC) capacity is an important feature common to all three-way catalysts to combat harmful exhaust emissions. To understand the mechanism of improved OSC for doped CeO2, we undertook the structural investigation by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H-2-TPR (temperature-programmed hydrogen reduction) and density functional theoretical (DFT) calculations of transition-metal-, noble-metal-, and rare-earth (RE)-ion-substituted ceria. In this report, we present the relationship between the OSC and structural changes induced by the dopant ion in CeO2. Transition metal and noble metal ion substitution in ceria greatly enhances the reducibility of Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu, Pd, Pt, Ru), whereas rare-earth-ion-substituted Ce(1-x)A(x)O(2-delta) (A = La, Y) have very little effect in improving the OSC. Our simulated optimized structure shows deviation in cation oxygen bond length from ideal bond length of 2.34 angstrom (for CeO2). For example, our theoretical calculation for Ce28Mn4O62 structure shows that Mn-O bonds are in 4 + 2 coordination with average bond lengths of 2.0 and 3.06 angstrom respectively. Although the four short Mn-O bond lengths spans the bond distance region of Mn2O3, the other two Mn-O bonds are moved to longer distances. The dopant transition and noble metal ions also affects Ce coordination shell and results in the formation of longer Ce-O bonds as well. Thus longer cation oxygen bonds for both dopant and host ions results in enhanced synergistic reduction of the solid solution. With Pd ion substitution in Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu) further enhancement in OSC is observed in H-2-TPR. This effect is reflected in our model calculations by the presence of still longer bonds compared to the model without Pd ion doping. The synergistic effect is therefore due to enhanced reducibility of both dopant and host ion induced due to structural distortion of fluorite lattice in presence of dopant ion. For RE ions (RE = Y, La), our calculations show very little deviation of bonds lengths from ideal fluorite structure. The absence of longer Y-O/La-O and Ce-O bonds make the structure much less susceptible to reduction.

Synthesis, Structure and Optical Studies of a Family of Three-Dimensional Rare-Earth Aminoisophthalates M(mu(2)-OH)(C8H5NO4)] (M = Y3+, La3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Dy3+, and Er3+)

A hydrothermal reaction of the acetate salts of the rare-earths, 5-aminoisophthalic acid (H(2)AIP), and NaOH at 150 degrees C for 3 days gave rise to a new family of three-dimensional rare-earth aminoisophthalates, M(mu(2)-OH)(C8H5NO4)] M = Y3+ (I), La3+ (II), Pr3+ (III), Nd3+ (IV), Sm3+ (V), Eu3+ (VI), Gd3+ (VII), Dy3+ (VIII), and Er3+ (IX)]. The structures contain M-O(H)-M chains connected by AIP anions. The AIP ions are connected to five metal centers and each metal center is connected with five AIP anions giving rise to a unique (5,5) net. To the best of our knowledge, this is the first observation of a (5,5) net in metal-organic frameworks that involve rare-earth elements. The doping of Eu3+/(3+) ions in place of Y3+/ La3+ in the parent structures gave rise to characteristic metal-centered emission (red = Eu3+, green = Tb3+). Life-time studies indicated that the excited emission states in the case of Eu3+ (4 mol-% doped) are in the range 0.287-0.490 ms and for Tb3+ (4 mol-% doped) are in the range of 1.265-1.702 ms. The Nd3+-containing compound exhibits up-conversion behavior based on two-photon absorption when excited using lambda = 580 nm.

Studies of cryotreatment on the performance of integral diaphragm pressure transducers for space application

The integral diaphragm pressure transducers machined out of precipitation hardened martensite stainless steel (APX4) are widely used for propellant pressure measurements in space applications. These transducers are expected to exhibit dimensional stability and linearity for their entire useful life. These vital factors are very critical for the reliable performance and dependability of the pressure transducers. However, these transducers invariably develop internal stresses during various stages of machining. These stresses have an adverse effect on the performance of the transducers causing deviation from linearity. In order to eliminate these possibilities, it was planned to cryotreat the machined transducers to improve both the long-term linearity and dimensional stability. To study these effects, an experimental cryotreatment unit was designed and developed based on the concept of indirect cooling using the concept of cold nitrogen gas forced closed loop convection currents. The system has the capability of cryotreating large number of samples for varied rates of cooling, soaking and warm-up. After obtaining the initial levels of residual stress and retained austenite using X-ray diffraction techniques, the pressure transducers were cryotreated at 98 K for 36 h. Immediately after cryotreatment, the transducers were tempered at 510 degrees C for 3 h in vacuum furnace. Results after cryo treatment clearly indicated significant reduction in residual stress levels and conversion of retained austenite to martensite. These changes have brought in improvements in long term zero drift and dimensional stability. The cryotreated pressure transducers have been incorporated for actual space applications. (c) 2010 Published by Elsevier Ltd.