The study of oxidation state of manganese in lead oxyhalide glasses by optical spectroscopy

Abstaract is not available.

Influence of Sm2O3 doping on formation and structure of SrBi2Nb2O9 nanocrystals in lithium borate glasses

New glasses of 16.66SrO–16.66[(1 − x)Bi2O3–xSm2O3]–16.66Nb2O5–50Li2B4O7 (0 ≤ x ≤ 0.5, in molar ratio), i.e., the pseudo-binary Sm2O3-doped SrBi2Nb2O9–Li2B4O7 glass system, giving the crystallization of Sm3+-doped SrBi2Nb2O9 nanocrystals are developed. It is found that the thermal stability of the glasses against the crystallization and the optical band gap energy increases with increasing Sm2O3 content. The formation of fluorite-type Sm3+-doped SrBi2Nb2O9 nanocrystals (diameters: 13–37 nm) with a cubic structure is confirmed in the crystallized (530 °C, 3 h) samples from X-ray powder diffraction analyses, Raman scattering spectrum measurements, and transmission electron microscope observations. The effect of Sm3+-doping on the microstructure, Raman scattering peak positions, and dielectric properties of composites comprising of fluorite-type SrBi2Nb2O9 nanocrystals and the Li2B4O7 glassy phase is clarified. It is found that fluorite-type SrBi2Nb2O9 nanocrystals transform to stable perovskite-type SrBi2Nb2O9 crystals with an orthorhombic structure by heat treatments at around 630 °C.

Chemical ordering in As-Se glasses: X-ray absorption edge and XPES studies

X-ray absorption edge and X-ray photoelectron spectroscopic studies of As-Se glasses seem to support a chemical ordering model.

An explanation for the rare occurrence of cis peptide units in proteins and polypeptides

The rarity of occurrence of cis peptide units is only partially explained by the higher intrinsic energy of the cis over the trans form, which provides a probability of 0·01 for cis peptide units to occur. An additional factor is the conformational restriction imposed by the occurrence of a cis peptide unit in a chain of trans units. Taking a section of three peptide units having the sequences trans-trans-trans (ttt) and trans-cis-trans (tct), conformational energy calculations indicate that the latter can occur only to an extent of 0·1%, unless there occurs the sequence X-Pro, in which case it is of the order of 30%. This explains the extreme rarity of cis peptide units, in general; however, it follows that even with non-prolyl residues, cis peptide units are not forbidden, but can occur in some rare examples and should be looked for.

Lanthanide coordination in dimethyl sulphoxide and antipyrine complexes of rare earth nitrates

Abstract is not available.

Itinerant electron ferromagnetism in Sr2+-, Ca2+-, and Ba2+-doped rare-earth orthocobaltites (Ln3+1�xM2+xCoO3)

Electronic and magnetic properties of Ln1�xSrxCoO3 (Ln = Pr, Nd, Sm, Eu, and Gd) systems show that above a critical value of x, the d electrons become itinerant while the materials become ferromagnetic at low temperatures. The ferromagnetic component increases with increase in x and decrease in temperature. The Curie temperature increases with x and decreases with decrease in the size of the rare-earth ion. Incorporation of Ba2+ in LaCoO3 favors itinerant electron ferromagnetism relative to Sr2+ while Ca2+ is less favorable than Sr2+.

Ferromagnetic resonance in Sr2+ doped rare earth orthocobaltites, Ln1â xSrxCoO3

FMR measurements have been carried out on several members of the Ln1âxSrxCoO3 (Ln = Rare earth) system. The results show that geff in these systems is around 1.25 independent of x as well as the rare earth ion. It is suggested that this unusual value of geff is due to the localized intermediate-spin Co3+ ions (t52ge1g) located at the top of the Ï* band.

Rapid quenching and glass formation in chalcogenide glasses: Preparation and properties of Ge-As-Te glasses over an extended composition ranges

In Ge-As-Te system, the glass forming region determined by normal melt quenching method has two regions (GFR I and GFR II) separated by few compositions gap. With a simple laboratory built twin roller apparatus, we have succeeded in preparing Ge7.5AsxTe92.5-x glasses over extended composition ranges. A distinct change in T-g is observed at x = 40, exactly at which the separation of the glass forming regions occur indicating the changes in the connectivity and the rigidity of the structural network. The maximum observed in glass transition (T-g) at x = 55 corresponding to the average coordination number (Z(av)) = 2.70 is an evidence for the shift of the rigidity percolation threshold (RPT) from Z(av) = 2.40 as predicted by the recent theories. The glass forming tendency (K-gl) and Delta T (=T-c-T-g) is low for the glasses in the GFR I and high for the glasses in the GFR II.

Evidence of an intermediate phase in ternary Ge7Se93-xSbx glasses

The compositional dependence of thermal properties, such as glass transition temperature (T-g), non-reversing enthalpy change (Delta H-NR) and the specific heat capacity change (Delta C-p) of melt quenched Ge7Se93-xSbx (21 a parts per thousand currency sign x a parts per thousand currency sign 31) glasses, has been studied using alternating differential scanning calorimetry (ADSC) which is analogous to modulated differential scanning calorimetry (MDSC). The glass transition temperature, T-g, which is a measure of global connectivity of the glass, has been found to increase with the addition of Sb. In addition, a change in slope has been observed in the composition dependence of T-g at an average coordination aOE (c) r > = 2.40. The experimentally observed compositional variation of glass transition temperature, has been compared with the theoretical predictions from the stochastic agglomeration theory (SAT) and has been found to be consistent. Further, a narrow thermally reversing window is seen in the compositional variation of the relaxation enthalpy (Delta H-NR), which is centered around aOE (c) r > = 2.40. The change in specific heat capacity (Delta C-p) at T-g is also found to exhibit a distinct minima at aOE (c) r > = 2.40, suggesting that the structural rearrangements for the liquid in the glass transition region are minimized around aOE (c) r > = 2.4.

Glass transitions in arsenic-selenium glasses

Glaiis transitions of As-Se glasses have been investigated over a wide range of compositions by using differential scanning calorimetry. The variation of Tg with composition has been interpreted on the basis of a bond-lattice model.

Spinodal Decomposition in Tellurite-Based Glasses Induced by Excimer Laser Irradiation

Tellurite-based glasses in the TeO2-K3Li2Nb5O15, TeO2-Ba5Li2Ti2Nb8O30, and V2Te2O9 were fabricated by the conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via the X-ray powder diffraction technique and differential thermal analysis, respectively. The as-quenched samples were irradiated by an excimer laser (248 nm). The effect of laser power, duration of irradiation, and the frequency of the laser pulses on the surface features of the above glasses were studied. The optical microscopic studies carried out on the above systems revealed the presence of quasi-periodic and periodic structures on their surfaces. The local compositional variations of these structures were confirmed by back-scattered electron imaging using scanning electron microscope accompanied by energy-dispersive X-ray analysis. These results were convincing enough to state that the glasses in the present investigations had undergone spinodal decomposition on laser irradiation. The incidence of the interconnected texture of two different phases was observed owing to the quenching effect produced by the heating and cooling cycle of the successive laser pulses. Ring- and line-shaped patterns were also observed, respectively, when the pulse frequency of the laser and the duration of irradiation were increased.

Mixed mode (I and II) crack tip fields in bulk metallic glasses

Stationary crack tip fields in bulk metallic glasses under mixed mode (I and II) loading are studied through detailed finite element simulations assuming plane strain, small scale yielding conditions. The influence of internal friction or pressure sensitivity on the plastic zones. notch deformation, stress and plastic strain fields is examined for different mode mixities. Under mixed mode loading, the notch deforms into a shape such that one part of its surface sharpens while the other part blunts. Increase in mode If component of loading dramatically enhances the normalized plastic zone size, lowers the stresses but significantly elevates the plastic strain levels near the notch tip. Higher internal friction reduces the peak tangential stress but increases the plastic strain and stretching near the blunted part of the notch. The simulated shear bands are straight and extend over a long distance ahead of the notch tip under mode II dominant loading. The possible variations of fracture toughness with mode mixity corresponding to failure by brittle micro-cracking and ductile shear banding are predicted employing two simple fracture criteria. The salient results from finite element simulations are validated by comparison with those from mixed mode (I and II) fracture experiments on a Zr-based bulk metallic glass.

Possible mechanism of charge transport and dielectric relaxation in SrO-Bi2O3-B2O3 glasses

Transparent SrBi2B2O7 glasses were prepared via melt-quenching technique and characterized using differential scanning calorimetry and x-ray powder diffraction. The ac conductivities of the glasses were studied as a function of frequency (100 Hz-10 MHz) at different temperatures. The frequency dependence of conductivity has been analyzed using Almond-West expression. The exponent n was nearly unaffected by temperature. Impedance and modulus spectroscopies were employed to further examine the electrical data. Dielectric relaxation exhibited a stretched exponential behavior with a stretching exponent beta independent of temperature. From conductivity analysis we have proposed that the charge transport occurs through the participation of nonbridging oxygen (NBO), which switches positions in a facile manner. The stretched exponential behavior appears to be a direct consequence of the NBO switching mechanism of charge transport.

Thermal anomalies in ternary Ge42-xPbxSe58 glasses near the charge carrier reversal threshold

The carrier type reversal (CTR) from p- to n-type in semiconducting chalcogenide glasses is an important and a long standing problem in glass science. Ge-Se glasses exhibit CTR when the metallic elements Bi and Pb are added. For example, bulk Ge42-xSe58Pbx glasses exhibit CTR around 8-9 at. % of Pb. These glasses have been prepared by melt quenching method. Glass transition temperature (T-g), Specific heat change between the liquid and the glassy states (Delta C-p) at T-g and the nonreversing heat flow (Delta H-nr) measured by modulated differential scanning calorimetry exhibit anomalies at 9 at. % of Pb. These observed anomalies are interpreted on the basis of the nano scale phase separation occurring in these glasses.