Design and fabrication of an automated temperature programmed reaction system to evaluate 3-way catalysts Ce1-x-y(La/Y)(x)PtyO2-delta

A completely automated temperature-programmed reaction (TPR) system for carrying out gas-solid catalytic reactions under atmospheric flow conditions is fabricated to study CO and hydrocarbon oxidation, and NO reduction. The system consists of an all-stainless steel UHV system, quadrupole mass spectrometer SX200 (VG Scientific), a tubular furnace and micro-reactor, a temperature controller, a versatile gas handling system, and a data acquisition and analysis system. The performance of the system has been tested under standard experimental conditions for CO oxidation over well-characterized Ce1-x-y(La/Y)(y)O2-delta catalysts. Testing of 3-way catalysis with CO, NO and C2H2 to convert to CO2, N-2 and H2O is done with this catalyst which shows complete removal of pollutants below 325 degrees C. Fixed oxide-ion defects in Pt substituted Ce1-y(La/Y)(y)O2-y/2 show higher catalytic activity than Pt ion-substituted CeO2

Heisenberg-like critical properties in ferromagnetic Nd1-xPbxMnO3 single crystals

Static magnetization for single crystals of insulating Nd0.85Pb0.15MnO3 and marginally conducting Nd0.70Pb0.30MnO3 has been studied around the ferromagnetic to paramagnetic transition temperature T-C. Results of measurements carried out in the critical range vertical bar(T - T-C)/T-C vertical bar <= 0.1 are reported. Critical exponents beta and gamma for the thermal behaviour of magnetization and susceptibility have been obtained both by modified Arrott plots and the Kouvel-Fisher method. The exponent delta independently obtained from the critical isotherm was found to satisfy the Widom scaling relation delta = gamma/beta + 1. For both compositions the values of exponents are consistent with those expected for isotropic magnets belonging to the Heisenberg universality class with short-range exchange in three dimensions. Correspondingly, the specific heat displays only a cusp-like anomaly at the critical temperature of these crystals which is consistent with an exponent alpha < 0. The results show that the ferromagnetic ordering transition in Nd1-xPbxMnO3 in the composition range 0.15 <= x <= 0.40 is continuous. This mixed-valent manganite displays the conventional properties of a Heisenberg-like ferromagnet, irrespective of the differing transport properties and in spite of low ordering temperatures T-C = 109 and 147.2 K for x = 0.15 and 0.30, respectively.

Low-temperature polymer precursor-based synthesis of nanocrystalline particles of lanthanum calcium manganese oxide (La0.67Ca0.33MnO3) with enhanced ferromagnetic transition temperature

We report a simple modified polymeric precursor route for the synthesis of highly crystalline and homogenous nanoparticles of lanthanum calcium manganese oxide (LCMO). The LCMO phase formation was studied by thermal analysis, x-ray powder diffraction, and infrared spectroscopy at different stages of heating. These nanocrystallites (average particle size of 30 nm) possess ferromagnetic-paramagnetic transition temperature (T-c) of 300 K, nearly 50 K higher than that of a single crystal. The Rietveld analysis of the powder x-ray diffraction data of the nanopowders reveals significant lattice contraction and reduction in unit cell anisotropy-these structural changes are correlated to the enhancement in T-c.

Influence of lattice distortion on the Curie temperature and spin-phonon coupling in LaMn0.5Co0.5O3

Two distinct ferromagnetic phases of LaMn0.5Co0.5O3 having monoclinic structure with distinct physical properties have been studied. The ferromagnetic ordering temperature T-c is found to be different for both the phases. The origin of such contrasting characteristics is assigned to the changes in the distance(s) and angle(s) between Mn-O-Co resulting from distortions observed from neutron diffraction studies. Investigations on the temperature dependent Raman spectroscopy provide evidence for such structural characteristics, which affects the exchange interaction. The difference in B-site ordering which is evident from the neutron diffraction is also responsible for the difference in T-c. Raman scattering suggests the presence of spin-phonon coupling for both the phases around the T-c. Electrical transport properties of both the phases have been investigated based on the lattice distortion.

A simple apparatus for the measurement of thermoelectric power in the temperature range 4·2–300K

A simple apparatus to measure the absolute thermoelectric power of solids in the temperature range 4·2–300K is described. The cryostat and the associated instrumentation is simple to operate. Representative data of measurements on metallic wire and pressed pellets are given. An accuracy of better than 10% in absolute thermopower can be obtained in this apparatus.

Natural Convection on a Horizontal Cone in a Porous Medium with Non-Uniform Wall Temperature/Concentration or Heat/Mass Flux and Suction/Injection

The steady natural convection flow on a horizontal cone embedded in a saturated porous medium with non-uniform wall temperature/concentration or heat/mass flux and suction/injection has been investigated. Non-similar solutions have been obtained. The nonlinear couple differential equations under boundary layer approximations governing the flow have been numerically solved. The Nusselt and Sherwood numbers are found to depend on the buoyancy forces, suction/injection rates, variation of wall temperature/concentration or heat/mass flux, Lewis number and the non-Darcy parameter.

Hydrolysis of Organophosphate Esters: Phosphotriesterase Activity of Metallo-beta-lactamase and Its Functional Mimics

The phosphotriesterase (PTE) activity of a series of binuclear and mononuclear zinc(II) complexes and metallo-beta-lactamase (m beta 1) from Bacillus cereus was studied. The binuclear complex 1, which exhibits good m beta 1 activity, shows poor PTE activity. In contrast,complex 2, a poor mimic of m beta 1, exhibits much higher activity than 1 The replacement of Cl- ligands by OH- is important for the high PTE activity of complex 2 because this complex does not show any catalytic activity in methanol. The natural enzyme m beta 1 from B. cereus is also found to be an inefficient catalyst in the hydrolysis of phosphotriesters. These observations indicate that the binding of beta-lactam substrates at the binuclear zinc(II) center is different from that of phosphotriesters. Furthermore, phosphodiesters, the products from the hydrolysis of triesters, significantly inhibit the PTE activity of m beta 1 and its functional mimics. Although the mononuclear complexes 3 and 4 exhibited significant m beta 1 activity, these complexes are found to be almost inactive in the hydrolysis of phosphotriesters. These observations indicate that the elimination of phosphodiesters from the reaction site is important for the PTE activity of zinc(II) complexes.

Continuous-cooling method of specific heat measurement in the temperature range 100-300 K

The authors have developed a simple continuous-cooling method to determine specific heat of liquids and solids in the temperature range 100-300 K. The technique employs very simple instrumentation and continuously records the sample temperature as it cools to the bath temperature through a calibrated heat link. They have obtained specific heat values which agree with the reported data to within 3% for the samples investigated. This method also facilitates easy detection of abrupt changes in specific heat, as demonstrated in the observation of glass transition in some organic glass-forming systems. The method is sensitive to the study of relaxing heat capacity in supercooled liquids.

Preparation and characterization of rubidium-beta-alumina by the gel-to-crystallite conversion method

Preparation of Rb-beta -alumina was realized by the gel-to-crystallite conversion method. Reaction of hydrated aluminum hydroxide gel with RbOH in ethanol medium gave rise to the Rb+-inserted pseudoboehmite precursor under wet chemical conditions. The thermal decomposition of the precursor yielded Rb-beta -alumina. The Rb2O:Al2O3 ratio of monophasic Rb-beta -alumina ranged from 1:10 to 1:22. The extended stability in the compositional range is due to the fact that the conduction planes containing Rb+ and O2- ions can have lower occupancy of Rb+ ions for larger sized alkali ions, permitting the steric separation of the adjoining spinel blocks. High-resolution electron microscopy revealed that the decreasing occupancy of alkali ions in the conduction plane is balanced by changing widths of spinel blocks arising from the shift of tetrahedral Al3+ ions to octahedral sites and an accompanying increase in stacking defects. (C) 2000 Elsevier Science Ltd. All rights reserved.

On the paradoxical relation between the melting temperature and forbidden energy gap of nanoparticles

We comment on the paradox that seems to exist about a correlation between the size-dependent melting temperature and the forbidden energy gap of nanoparticles. By analyzing the reported expressions for the melting temperature and the band gap of nanoparticles, we conclude that there exists a relation between these two physical quantities. However, the variations of these two quantities with size for semiconductors are different from that of metals. (C) 2010 American Institute of Physics.[doi:10.1063/1.3466920].

Electron microscopic investigation of high-temperature oxide superconductors

Electron microscopic investigations have been carried out on superconducting YBa2Cu3 O7−δ, NdBa2Cu3 O7−δ and related oxides. All these orthorhombic oxides exhibit twin domains. Based on high resolution electron microscopy, it is shown that there is no significant change in the structure across the twins. Oxides of the La2−x Sr x (Ba x )CuO4 system do not show twins, but exhibit other types of defects. Twins appear to be characteristic of only the orthorhombic 123 structures.

Ability of human chorionic gonadotropin beta-subunit to inhibit the steroidogenic response to lutropin

Ability of the beta-subunit of human chorionic gonadotropin to inhibit the response to lutropin (luteinizing hormone, LH) was tested in the immature rat ovarian system and pregnant-mare-serum-gonadotropin-primed rat ovarian system with progesterone production being used as the response. Human chorionic gonadotropin beta-subunit was found to inhibit human and ovine lutropin-stimulated progesterone production. At a constant dose of lutropin, inhibition was dependent on the concentration of beta-subunit. When concentration of the beta-subunit was kept constant at 5.0 microgram/ml and the concentration of lutropin was varied, the inhibition was maximum at the saturating concentration of the native hormone. The alpha-subunit of the human chorionic gonadotropin did not inhibit the response to lutropin. The lutropin/beta-subunit ratio required to produce an inhibition of response was much lower than that required to bring about an observable inhibition of binding.

High-temperature superconductivity in bismuth-copper oxides of the type BimMnCupOx (M=Mg, Ca, Sr, Ba, Bi)

Several oxides of the Bi m M n Cu p O x family (m=2, 3;n=2, 3, 4;p=1, 2, 3 and M=alkaline earth or Bi), possessing structures similar to the Aurivillius family of oxides, show highT c superconductivity.