Combustion synthesis of rare earth cuprates

Rare earth cuprates, La2CuO4 Nd2CuO4, La1.8M0.2CuO4 (M=Ca.Sr) and Nd1.85Ce0.15CuO4 have been prepared by the combustion of redox mixtures containing corresponding metal nitrates and maleic hydrazide, C4H4N2O2, at 350°C. The solid combustion products are submicron size amorphous powders which on heat treatment (700°C, 30 minutes) yield crystalline single phase cuprates. Strontium doped lanthanum cuprate, La1.8Sr0.2CuO4, shows an onset of superconductivity at 36K.

Metal-Insulator Transitions in Anion-Excess LaMnO3+? Controlled by the Mn4+ Content

LaMnO3+? samples with Mn4+ content up to 50% have been prepared by different methods. The structure of LaMnO3+? changes from orthorhombic to cubic (via rhombohedral) with increase in the Mn4+ content. LaMnO3+? samples containing greater than 20% Mn4+ are ferromagnetic and show resistivity maxima at a temperature Tt which is close to the ferromagnetic Curie temperature. The resistivity maximum is due to the occurrence of a metal-insulator transition. In samples heated to the same temperature, the value of Tt increases with % Mn4+. For a given sample, Tt increases with the temperature of heat treatment due to the increase in particle size. The onset of ferromagnetism in LaMnO3+? accompanied by an insulator-metal transition is similar to that found in La1-xCaxMnO3 and La1-xSrxCoO3.

Chromium-manganese iron alloy system design cast in metal and sand moulds for erosion resistance: a positron lifetime study

Erosion characteristics of high chromium (Cr, 16-19%) alloy cast iron with 5% and 10% manganese (Mn) prepared in metal and sand moulds through induction melting are investigated using jet erosion test setup in both as-cast and heat-treated conditions. The samples were characterised for hardness and microstructural properties. A new and novel non-destructive evaluation technique namely positron lifetime spectroscopy has also been used for the first time to characterise the microstructure of the material in terms of defects and their concentration. We found that the hardness decreases irrespective of the sample condition when the mould type is changed from metal to sand, On the other hand, the erosion volume loss shows an increasing trend. Since the macroscopic properties have a bearing on the microstructure, good credence is obtained from the microstructural features as seen from light and scanning electron micrographs. Faster cooling in the metal mould yielded fine carbide precipitation on the surface. The defect size and their concentration derived from positron method are higher for sand mould compared to metal mould. Lower erosion loss corresponds to smaller size defects in metal mould are the results of quicker heat transfer in the metal mould compared to the sand mould. Heat treatment effects are clearly seen as the reduced concentration of defects and spherodisation of carbides points to this. The erosion loss with respect to the defects size and concentration correlate very well.

Characterization of a 10- to 14-kilodalton protease-sensitive mycobacterium tuberculosis H37Ra antigen that stimulates human -yi T cells

gamma delta T-cell receptor-bearing T cells (gamma delta T cells) are readily activated by intracellular bacterial pathogens such as Mycobacterium tuberculosis. The bacterial antigens responsible for gamma delta T-cell activation remain poorly characterized. We have found that heat treatment of live M. tuberculosis bacilli released into the supernatant an antigen which stimulated human gamma delta T cells, gamma delta T-cell activation was measured by determining the increase in percentage of gamma delta T cells by flow cytometry in peripheral blood mononuclear cells stimulated with antigen and by proliferation of gamma delta T-cell lines with monocytes as antigen-presenting cells. Supernatant from heat-treated M. tuberculosis was fractionated by fast-performance liquid chromatography (FPLC) on a Superose 12 column. Maximal gamma delta T-cell activation was measured for a fraction of 10 to 14 kDa. Separation of the supernatant by preparative isoelectric focusing demonstrated peak activity at a pi of <4.0. On two-dimensional gel electrophoresis, the 10- to 14-kDa FPLC fraction contained at least seven distinct molecules, of which two had a pi of <4.5. Protease treatment reduced the bioactivity of the 10- to 14-kDa FPLC fraction for both resting and activated gamma delta T cells. Murine antibodies raised to the 10- to 14-kDa fraction reacted by enzyme-linked immunosorbent assay with antigens of 10 to 14 kDa in lysate of M. tuberculosis. In addition, gamma delta T cells proliferated in response to an antigen of 10 to 14 kDa present in M. tuberculosis lysate. gamma delta T-cell-stimulating antigen was not found in culture filtrate of M. tuberculosis but was associated,vith the bacterial pellet and lysate of M. tuberculosis. These results provide a preliminary characterization of a 10- to 14-kDa, cell-associated, heat-stable, low-pI protein antigen of M. tuberculosis which is a major stimulus for human gamma delta T cells.

Heuristic algorithms for scheduling of a batch processor in automobile gear manufacturing

In this paper we address a scheduling problem for minimising total weighted tardiness. The motivation for the paper comes from the automobile gear manufacturing process. We consider the bottleneck operation of heat treatment stage of gear manufacturing. Real life scenarios like unequal release times, incompatible job families, non-identical job sizes and allowance for job splitting have been considered. A mathematical model taking into account dynamic starting conditions has been developed. Due to the NP-hard nature of the problem, a few heuristic algorithms have been proposed. The performance of the proposed heuristic algorithms is evaluated: (a) in comparison with optimal solution for small size problem instances, and (b) in comparison with `estimated optimal solution' for large size problem instances. Extensive computational analyses reveal that the proposed heuristic algorithms are capable of consistently obtaining near-optimal solutions (that is, statistically estimated one) in very reasonable computational time.

Role of zirconium addition on stability of UAl3 phase in Al-U system

The microstructural changes of Al-22 wt%U and Al-46 wt%U alloys containing 3 wt% Zr were investigated after heat treatment at 620 degrees C for 1 to 45 days, Though it is reported that addition of similar to 3 wt% Zr stabilizes the (U,Zr)Al-3 phase at room temperature, the present investigation shows that the (U,Zr)Al-3 phase is not stable but slowly transforms to the U0.9Al4 phase, The high temperature creep curves generated for these ternary alloys showed a wavy pattern which also suggests that the (U,Zr)Al-3 phase is not stable.

Hydrothermal synthesis, characterization and Raman studies of Eu3+ activated Gd2O3 nanorods

Eu3+ (8 mol%) activated gadolinium oxide nanorods have been prepared by hydrothermal method without and with surfactant, cityl trimethyl ammonium bromide (CTAB). Powder X-ray diffraction (PXRD) studies reveal that the as-formed product is in hexagonal Gd(OH)(3):Eu phase and subsequent heat treatment at 350 and 600 degrees C transforms the sample to monoclinic GdOOH:Eu and cubic Gd2O3:Eu phases, respectively. The structural data and refinement parameters for cubic Gd2O3:Eu nanorods were calculated by the Rietveld refinement. SEM and TEM micrographs show that as-obtained Gd(OH)(3):Eu consists of uniform nanorods in high yield with uniform diameters of about 15 nm and lengths of about 50-150 nm. The temperature dependent morphological evolution of Gd2O3:Eu without and with CTAB surfactant was studied. FTIR studies reveal that CTAB surfactant plays an important role in converting cubic Gd2O3:Eu to hexagonal Gd(OH)(3):Eu. The strong and intense Raman peak at 489 cm(-1) has been assigned to A(g) mode, which is attributed to the hexagonal phase of Gd2O3. The peak at similar to 360 cm(-1) has been assigned to the combination of F-g and E-g modes, which is mainly attributed to the cubic Gd2O3 phase. The shift in frequency and broadening of the Raman modes have been attributed to the decrease in crystallite dimension to the nanometer scale as a result of phonon confinement. (C) 2010 Elsevier B.V. All rights reserved.

Metastable phase relations and europium(II) luminescence of barium hexa-aluminates prepared by gel to crystallite conversion

Wet chemical reaction of hydrated alumina gels, Al2O3.yH(2)O(80treatment above 1600 degrees C, indicating the subsolidus decomposition to 0.82BaO 6Al(2)O3 and 1.32BaO 6Al(2)O(3). High resolution electron microscopy reveals extensive distribution of the blocking defects and structural intergrowths. The metastable Ba-hexa-aluminates doped with Eu(II), exhibit predominantly the 436nm emission band for all the 'x' values. No deterioration in emission intensity is noticed on long term preservation of the phosphors. Differences prevailing in literature on the phase relations in Ba-hexa-aluminates can be attributed to preparative route dependent metastability.

Preparation of the layered double hydroxide (LDH) LiAl2(OH)(7)center dot 2H(2)O, by gel to crystallite conversion and a hydrothermal method, and its conversion to lithium aluminates

A layered double hydroxide (LDH) with chemical composition LiAl2(OH)(7) . 2H(2)O was prepared via a wet chemical route of gel to crystallite (G-C) conversion at 80 degrees C involving the reaction of hydrated alumina gel, Al2O3.yH(2)O (80 < y < 120) with LiOH (Li2O/Al2O3 greater than or equal to 0.5) in presence of hydrophilic solvents such as ethanol under refluxing conditions. The hydrothermal synthesis was carried out using the same reactants by heating to less than or equal to 140 degrees C in a Teflon-lined autoclave under autogenerated pressure (less than or equal to 20 MPa). Transmission electron microscopy showed needle-shaped aggregates of size 0.04-0.1 mu m for the gel to crystallite conversion product, whereas the hydrothermal products consisted of individual lamellar crystallites of size 0.2-0.5 mu m with hexagonal morphology. The LDH prepared through the gel to crystallite conversion could be converted into LiAl(OH)(4) . H2O or LiAl(OH)(3)NO3 . H2O by imbibition of LiOH or LiNO3, respectively, under hydrothermal conditions. Thermal decomposition of LDH above 1400 degrees C gave rise to LiAl5O8 accompanied by the evaporation of Li2O. LiAl(OH)(4) . H2O and LiAl(OH)(3)NO3 . H2O decomposed in the temperature range 400-1000 degrees C to alpha- or beta-LiAlO2. The compositional dependence of the product, the intermediate phases formed during the heat treatment and the possible reactions involved are described in detail.

Synthesis of nanodispersed phases during rapid solidification and crystallization of glasses in Ti75Ni25 alloys

The formation of the metallic glass and crystalline phases and related microstructures and the decomposition behavior of rapidly solidified Ti75Ni25 alloys obtained under different processing conditions have been investigated in detail. The competition between glass transition and nucleation of beta-Ti during rapid solidification leads to the possibility of synthesizing the nanocomposites of beta-Ti and glass. Additionally, it is shown that the presence of a small amount of Si also promotes simultaneous nucleation of fine Ti2Ni intermetallic compound. Thermodynamic calculation of the metastable phase diagram indicates the presence of a metastable eutectic reaction between alpha-Ti and Ti2Ni. Evidence of this reaction at lower cooling rates has been presented. On heating, the glass decomposes through this reaction. Finally, on the basis of understanding of the microstructural evolution during decomposition, a new approach has been adopted to synthesize a nanodispersed composite of alpha-Ti in the crystalline Ti2Ni matrix with a narrow size distribution by controlling the devitrification heat treatment of the metallic glass.

The effect of preaging on the delayed aging of Al-7Si-0.3Mg

Al-7Si-0.3Mg is a commonly used commercial casting alloy because of its excellent castability combined with good mechanical properties. The post-casting heat treatment is one factor that affects the mechanical properties; during heat treat ment, a delay between solutionizing and artificial aging (delayed aging) leads to a reduction in hardness, ultimate tensile strength, and yield strength in the alloy. The investigation reported here was aimed at understanding the extent to which the harmful effect of delayed aging on hardness/strength can be nullified. The results obtained were explained using Pashley's kinetic model.

Lithium borate-strontium bismuth tantalate glass nanocomposite: a novel material for nonlinear optic and ferroelectric applications

Glass nanocomposites in the system (100 - x)Li2B4O7-xSrBi(2)Ta(2)O(9) (0 less than or equal to x less than or equal to 22.5, in molar ratio) were fabricated via a melt quenching technique followed by controlled heat-treatment. The as-quenched samples were confirmed to be glassy and amorphous by differential thermal analysis (DTA) and X-ray powder diffraction (XRD) techniques, respectively. The phase formation and crystallite size of the heat-treated samples (glass nanocomposites) were monitored by XRD and transmission electron microscopy (TEM). The relative permittivities (epsilon(tau)') of the glass nanocomposites for different compositions were found to lie in between that of the parent host glass (Li2B4O7) and strontium bismuth tantalate (SBT) ceramic in the frequency range 100 Hz-40 MHz at 300 K, whereas the dielectric loss (D) of the glass nanocomposite was less than that of both the parent phases. Among the various dielectric models employed to predict the effective relative permittivity of the glass nanocomposite, the one obtained using the Maxwell's model was in good agreement with the experimentally observed value. Impedance analysis was employed to rationalize the electrical behavior of the glasses and glass nanocomposites. The pyroelectric response of the glasses and glass nanocomposites was monitored as a function of temperature and the pyroelectric coefficient for glass and glass nanocomposite (x = 20) at 300 K were 27 muC m(-2) K-1 and 53 muC m(-2) K-1, respectively. The ferroelectric behavior of these glass nanocomposites was established by P vs. E hysteresis loop studies. The remnant polarization (P-r) of the glass nanocomposite increases with increase in SBT content. The coercive field (E-c) and P-r for the glass nanocomposite (x = 20) were 727 V cm(-1) and 0.527 muC cm(-2), respectively. The optical transmission properties of these glass nanocomposites were found to be composition dependent. The refractive index (n = 1.722), optical polarizability (am = 1.266 6 10 23 cm 3) and third-order nonlinear optical susceptibility (x(3) = 3.046 6 10(-21) cm(3)) of the glass nanocomposite (x = 15) were larger than those of the as-quenched glass. Second harmonic generation (SHG) was observed in transparent glass nanocomposites and the d(eff) for the glass nanocomposite (x = 20) was found to be 0.373 pm V-1.

New transparent crystallized glasses with optical nonlinear LiBGeO4 crystals

Crystallization behaviors of the glass with a composition of 25Li(2)O.25B(2)O(3).50GeO(2) corresponding to lithium borogermanate LiBGeO4 have been examined. It has been confirmed that the LiBGeO4 crystalline phase is formed at the surface of heat-treated glasses. The second harmonic (SH) generation is found from transparent surface crystallized glasses, demonstrating for the first time that the LiBGeO4 phase shows optical nonlinearity. The SH intensity of LiBGeO4 crystallites (powdered state) prepared through crystallization is about ten times as large as that of pulverized alpha-quartz. The SH intensity of transparent crystallized glasses (bulk state) with crystalline layers of 3-4.5 mum thickness increases with increasing heat treatment temperature (540-560degreesC) and time (1-6 h), and the maximum SH intensity among the samples studied is in the order of 1/10 in comparison with that of alpha-quartz single crystal. The transparent crystallized glass obtained by heat treatment at 550alphaC for 3 h exhibits a clear and fine Maker fringe pattern, indicating a highly orientation of LiBGeO4 crystals at the surface.

Pyroelectric, ferroelectric and optical properties of glass nanocomposite: Lithium borate-bismuth tungstate

Glass nanocomposites in the system (1-x)Li2B4O7-xBi(2)WO(6) (0 less than or equal to x less than or equal to 0.35, in molar ratio) were fabricated by splat quenching technique. The as-quenched samples were X-ray amorphous. Differential Thermal Analyses (DTA) confirmed their glassy nature. The composites on heat-treatment at 720 K yielded monophasic crystalline bismuth tungstate in lithium borate glass matrix. The average size and the spherical nature of the dispersed crystallites were assessed via High Resolution Transmission Electron Microscopy (HRTEM). The dielectric constants (epsilon(r)) of both the as-quenched and post heat-treated composites were found to increase with increase in x (bismuth tungstate content) at all the frequencies (100 Hz-40 MHz) in the temperature range 300 K-870 K. While the dielectric loss (D) decreased with increasing x. The pyroelectric coefficients of the as-quenched (consisting 20 nm sized crystallites) and 720 K heat-treated sample (x = 0.3) were determined as a function of temperature (300 K-873 K) and the values obtained at room temperature were 20 and 60 muC/m(2) K respectively. The as-quenched and heat-treated (720 K) glass nanocomposites exhibited ferroelectric (P Vs E) hysteresis loops. The remnant polarization and coercive field of the heat-treated glass nanocomposite at 300 K were respectively 2.597 muC/cm(2) and 543 V/cm. These glass nanocomposites were birefringent in the 300-873 K temperature range.

Characterization of lithium borate–bismuth tungstate glasses and glass-ceramics by impedance spectroscopy

Transparent glasses in the system (1−x)Li2B4O7–xBi2WO6 (0≤x≤0.35) were prepared via melt quenching technique. Differential thermal analysis was employed to characterize the as-quenched glasses. Glass-ceramics with high optical transparency were obtained by controlled heat-treatment of the glasses at 720 K for 6 h. The amorphous nature of the as-quenched glass and crystallinity of glass-ceramics were confirmed by X-ray powder diffraction studies. High resolution transmission electron microscopy (HRTEM) shows the presence of nearly spherical nanocrystallites of Bi2WO6 in Li2B4O7 glass matrix. Capacitance and dielectric loss measurements were carried out as a function of temperature (300–870 K) in the frequency range 100 Hz–40 MHz. Impedance spectroscopy employed to rationalize the electrical behavior of glasses and glass-ceramics suggest the coexistence of electronic and ionic conduction in these materials. The thermal activation energies for the electronic conduction and ionic conduction were also estimated based on the Arrhenius plots.