Highly Monodisperse Colloidal Magnesium Nanoparticles by Room Temperature Digestive Ripening

Nanoclusters of 25 nm sized Mg-THF have been prepared by the solvated metal atom dispersion method. Room-temperature digestive ripening of these nanoclusters in the presence of hexadecylamine (HDA) resulted in highly monodisperse colloidal Mg-HDA nanoparticles of 2.8 ± 0.2 nm. An insight into the room-temperature digestive ripening process was obtained by studying the disintegration of clusters for various Mg:HDA ratios. The Mg colloids are quite stable with respect to precipitation of particles under Ar atmosphere. Using this procedure, pure Mg(0) nanopowders were obtained in gram scale quantities. The Mg powder precipitated from the colloid was fully hydrided at 33 bar and 118 °C. Initial desorption of H2 from samples of MgH2 was achieved at a remarkably low temperature, 115 °C compared to >350 °C in bulk Mg, demonstrating the importance of the size on the desorption temperatures.

Effect of Temperature Variation on Sister Chromatid Exchange Frequency in Cultured Human Lymphocytes

The effect of temperature variation on sister chromatid exchange (SCE) frequencies in human lymphocytes was studied. An increase as well as decrease in incubation temperature of cells leads to a higher frequency of sister chromatid exchanges than in cultures grown at 37°C. In addition, it was observed that mitotic: index and cell cycle duration were affected by low temperature.

1H NMR and a study of the anomalous temperature dependence of the 35Cl NQR frequencies in 2-chloro-3-pyridinol

A 35Cl NQR study of 2-chloro-3-pyridinol showed the presence of four NQR signals at 77 K. One of the lines showed a positive temperature coefficient of the NQR frequency. 1H NMR studies showed the presence of intramolecular hydrogen bonding, and the anomalous NQR temperature dependence has been explained in terms of Bayer and hydrogen bond effects. The room temperature x-ray structure and the low-temperature NQR data suggest the presence of a phase transition.

Time- and Temperature-Dependent Study in the Three-Component Zinc-Triazolate-Oxybis(benzoate) System: Stabilization of New Topologies

Three new three-dimensional zinc-triazolate-oxybis(benzoate) compounds. [{Zn-3(H2O)(2)}{C12H8O(COO)(2)}(2)-{C2H2N3}(2)]center dot 2H(2)O(I), [Zn-7{C12H8O(COO)(2)}(4){C2H2N3}(6)]center dot H2O, (II), and[{Zn-5(OH)(2)}{C12H8O(COO)(2)}(3){C2H2N3}(2)] (III), synthesized by a hydrothermal reaction of a mixture of Zn(OAc)(2)center dot 2H(2)O, 4,4'-oxybis(benzoic acid), 1,2,4-triazole, NaOH, and water. Compound I has an interpenetrated diamond structure and II and III have pillared-layer related structures. The formation of a hydrated phase (I) at low temperature and a completely dehydrated phase (III) at high temperature suggests the importance of thermodynamic factors in the formation of three compounds. Transformation studies of I in the presence of water shows the formation of a simple Zn-OBA compound, [Zn(OBA)(H2O)] (IV), at 150 and 180 degrees C and compound III at 200 degrees C. The compounds have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction. thermogravimetric analysis, IR, and photoluminescence studies.

Differential scanning calorimetric studies on ammonium perchlorate

Differential scanning calorimetric studies on ammonium perchlorate have been carried out. The enthalpy values for the phase transition endotherm and the two exotherms have been reported in the present communication. A new method has been developed for the estimation of kinetic parameters from DSC the mograms. The values for activation energy as calculated by the above method for low temperature and high temperature exotherms are in close agreement with literature values. The present studies also confirm the presence of small exothermic peaks at the initial stages of high temperature exotherm. Explanation for the same has been given.

Effect of temperature, pressure and additives on pyrolysis of polystyrene peroxide

Some aspects of the pyrolysis of polystyrene peroxide (PSP) have been examined. Low-temperature decomposition studies at 60°C and 70°C have been carried out to elucidate the ageing behaviour of PSP. The exothermic decomposition was found to be complete in 44 h at 70°C suggesting that all peroxide bonds have broken. Enthalpy measurements of the aged samples were carried out as a function of storage time. Ageing was also followed by infrared spectroscopy, and the intensity of the peroxide absorption around 1050 cm−1 was found to decrease with ageing time. Benzaldehyde formed as a result of PSP pyrolysis is readily converted into benzoic acid, which crystallizes during the ageing process. Pyrolysis—gas chromatographic studies have shown that up to 450°C the basic decomposition mechanism (i.e., the formation of benzaldehyde and formaldehyde as the major products) does not change. No effect of pressure on the decomposition exotherm in differential thermal analysis was observed, suggesting that peroxide composition involves only condensed phase reactions. Hydroquinone, p-aminophenol and cadmium sulphide were found to retard the thermal decomposition of PSP, suggesting that these compounds would be potential antioxidants for polymers.

Effect of manganese dioxide on the thermal decomposition of ammonium perchlorate

Thermal decomposition of powdered ammonium perchlorate, catalysed by manganese dioxide (MnO2), has been studied in the low concentration ranges of the catalyst. MnO2 sensitises the thermal decomposition of ammonium perchlorate. The activation energy estimations of catalysed ammonium perchlorate show that the value is about 30 kcal/mol throughout the low and the high temperature regions whereas uncatalysed ammonium perchlorate gives two activation energies, 20 kcal/mol in the low temperature region (280-320°C) and 60 kcal/mol in the higher temperature region (350-390°C). This behaviour has been explained on the basis of an electron transfer process. The effectiveness of MnO2 in the thermal decomposition further increases on pre-heating the sample at 50°C for two weeks; manganese ions enter the ammonium perchlorate lattice during the process of pre-heating.

Structural Investigation of Activated Lattice Oxygen in Ce1-xSnxO2 and Ce1-x-ySnxPdyO2-delta by EXAFS and DFT calculation

Substitution of Sn4+ ion in CeO2 creates activated oxygen in Ce0.8Sn0.2O2 leading to higher oxygen storage capacity compared to Ce0.8Zr0.2O2. With Pd ion substitution in Ce0.8Sn0.2O2,activation of oxygen is further enhanced as observed from the H-2/TPR study. Both EXAFS analysis and DFT calculation reveal that in the solid solution Ceexhibits 4 + 4 coordination, Sri exhibits 4 + 2 + 2 coordination and Pd has 4 + 3 coordination. While the oxygen in the First four coordination with short M-O bonds are strongly held in the lattice, the oxygens in the second and higher coordinations with long M-O bonds are weakly bound, and they are the activated oxygen ill the lattice. Bond valence analysis shows that oxygen with valencies as low its 1.65 are created by the Sn and Pd ion Substitution. Another interesting observation is that H-2/TPR experiment of Ce1-xSnxO2 shows a broad peak starting from 200 to 500 degrees C, while the same reduction is achieved in a single step at similar to 110 degrees C in presence Pd2+ on. Substitution of Pd2+ ion thus facilitates synergistic reduction of the catalyst at lower temperature. We have shown that simultaneous reduction of the Ce4+ and Sr4+ ions by Pd-0 is the synergistic interaction leading to high oxygen storage capacity at low temperature.

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.

Studies on the ionic transport and structural investigations of La0.5Li0.5TiO3 perovskite synthesized by wet chemical methods and the effect of Ce, Zr substitution at Ti site

La0.5Li0.5TiO3 perovskite was synthesized by various wet chemical methods. By adopting low temperature methods of preparation lithium loss from the material is prevented. La0.5Li0.5TiO3 (LLTO) was formed with cubic symmetry at 1473 K. LLTO was formed at relatively lower temperature by using hydrothermal preparation method. PVA gel-decomposition route yield tetragonal LLTO on annealing the dried gel at 1473 K. By using gel-carbonate route LiTi2O4 minor phase was found to remain even after heat-treatment at 1473 K. The hydroxylation of LLTO was done in deionized water as well as in dilute acetic acid medium. By hydroxylation process incorporation of hydroxyls and leaching out of Li+ was observed from the material. The Li+ concentration of these compositions was examined by AAS. The electrical conductivities of these compositions were measured by dc and ac impedance techniques at elevated temperatures. The activation energies of electrical conduction for these compositions were estimated from the experimental results. The measured activation energy of Li+ conduction is 0.34 eV. Unhydroxylated samples exhibit only Li+ conduction, whereas, the hydroxylated LLTO show proton conductivity at 298-550 K in addition to Li+ conductivity. The effect of Zr or Ce substitution in place of Ti were attempted. La0.5Li0.5ZrO3 Perovskite was not formed; instead pyrochlore phase (La2Zr2O7) along with monoclinic ZrO2 phases was observed above 1173 K; below 1173 K cubic ZrO2 is stable. (La0.5Li0.5)(2)CeO4 solid solution was formed in the case of Ce substitution at Ti sublattice on heat-treatment up to 1673 K. (c) 2005 Springer Science + Business Media, Inc.

Main chain and segmental dynamics of semi interpenetrating based on polyisoprene and poly(methyl methacrylate)

Main chain and segmental dynamics of polyisoprene (PI) and poly(methyl methacrylate)(PMMA) chains in semi IPNs were systematically studied over a wide range of temperatures (above and below T-g of both polymers) as a function of composition, crosslink density, and molecular weight. The immiscible polymers retained most of its characteristic molecular motion; however, the semi IPN synthesis resulted in dramatic changes in the motional behavior of both polymers due to the molecular level interpenetration between two polymer chains. ESR spin probe method was found to be sensitive to the concentration changes of PMMA in semi IPNs. Low temperature spectra showed the characteristics of rigid limit spectra, and in the range of 293-373 K.complex spectra were obtained with the slow component mostly arisingout of the PMMA rich regions and fast component from the PI phase. We found that the rigid PMMA chains closely interpenetrated into thehighly mobile PI network imparts motional restriction in nearby PI chains, and the highly mobile PI chains induce some degree of flexibility in highly rigid PMMA chains. Molecular level interchain mixing was found to be more efficient at a PMMA concentration of 35 wt.%. Moreover, the strong interphase formed in the above mentionedsemi IPN contributed to the large slow component in the ESR spectra at higher temperature. The shape of the spectra along with the data obtained from the simulations of spectra was correlated to the morphology of the semi IPNs. The correlation time measurement detected the motional region associated with the glass transition of PI and PMMA, and these regions were found to follow the same pattern of shifts in a-relaxation of PI and PMMA observed in DMA analysis. Activation energies associated with the T-g regions were also calculated. T-50G was found to correlate with the T-g of PMMA, and the volume of polymer segments undergoing glass transitional motion was calculated to be 1.7 nm(3).C-13 T-1 rho measurements of PMMA carbons indicate that the molecular level interactions were strong in semi IPN irrespective of the immiscible nature of polymers. The motional characteristics of H atoms attached to carbon atoms in both polymers were analyzed using 2D WISE NMR. Main relaxations of both components shifted inward, and both SEM and TEM analysis showed the development of a nanometer sized morphology in the case of highly crosslinked semi IPN. (C) 2010 Elsevier Ltd. All rights reserved.

A study of the slow reaction in Al-5 wt.% Ag alloy by resistivity measurements

The slow reaction in an Al-5 wt.% Ag alloy has been investigated by resistivity measurements. The "slope change" method gave an activation energy of 1.25 eV for silver diffusion during the slow reaction. The existence of an excess concentration of vacancies in equilibrium with the dislocation loops seems to be responsible for the slow reaction. The presence of silver inhibits the nucleation of dislocation loops by holding up the quenched-in vacancies in solution. There is no indication of the presence of a third stage in the low-temperature ageing process of this alloy.

Dislocation dynamics in alpha titanium Dynamique des dislocations dans le titane alphaVersetzungsdynamik in alpha-Titan

The activation area and activation enthalpy are determined as a function of stress and temperature for alpha titanium. The results indicated that plastic flow below about 700°K occurs by a single thermally activated mechanism. Activation area determined by differential-stress creep tests falls in the range 80−8b2 and does not systematically depend on the impurity content. The total activation enthalpy derived from the temperature and strain-rate dependence of flow stress is 1.15 eV. The experimental data support a lattice hardening mechanism as controlling the low-temperature deformation in alpha titanium.

NMR relaxation study of disorder in condensed matter: solid solutions of betaine phosphate and phosphite

Proton NMR relaxation measurements have been carried out in anti-ferroelectric Betaine phosphate (BP), ferroelectric Betaine phosphite (BPI) and the mixed system BPI(1-x)BPx, at 11.4MHz and 23.3MHz from 300K to 80K for x=0.0, 0.25, 0.45, 0.85, and 1.0. The temperature dependence of spin lattice relaxation time T, exhibits two minima as expected from the BPP model in BP and BPI. The Larmor frequency dependence of T, in the mixed system is rather unusual and exhibits different slopes for the low temperature wings at the two frequencies, which is a clear experimental evidence of the presence of different methyl groups with different activation energies (E-a) indicating disorder.

Annealing effect on transport properties of Nd0.67Sr0.33MnO3 thin films

Annealing dependence of the lattice parameter, resistivity, magnetoresistance and thermopower have been studied on Nd0.87Sr0.33MnO3 thin films deposited on LaAlO3 and alumina substrates by pulsed laser ablation. Upon annealing at 800 degrees C and 1000 degrees C the lattice constant of the LaAlO3 film tends toward that of the bulk target due to reduction in oxygen vacancies. This results in a metal-insulator transition at temperatures which increase with progressive annealing along with a decrease in the observed low temperature MR. Using a magnon scattering model we estimate the e(g) bandwidth of the film annealed at 1000 degrees C and show that the magnon contribution to the resistivity is suppressed in a highly oxygen deficient film and gains prominence only upon subsequent annealing. We also show that upon annealing, the polaron concentration and the spin cluster size increases in the paramagnetic phase, using an adiabatic polaron hopping model which takes into account an exchange dependent activation energy above the resistivity peak.