Combustion Synthesis and Properties of Fine Particle Spinel Manganites

Fine particle spinel manganites have been prepared by thermal decomposition of the precursors N2H5M1/3Mn2/3(N2H3COO)3 · H2O (M = Co and Ni) and M1/3 Mn2/3(N2H3COO)2 · 2H2O (M = Mg and Zn), as well as by the combustion of redox mixtures containing M(II) nitrate (M = Mg, Co, Ni, Cu, and Zn), Mn(II) nitrate, and maleic hydrazide (MH) in the required molar ratio. Both the precursor and redox mixtures undergo self-propagating, gas-producing, exothermic reactions once ignited at 250-375°C to yield corresponding manganites in less than 5 min. Formation of single phase products was confirmed by X-ray powder diffraction patterns. The manganites are of submicrometer size and have surface area in the range 20-76 m2/g.

Hydrazine carboxylate precursors to fine particle titania, zirconia and zirconium titanate

Titanyl hydrazine carboxylate dihydrate, TiO(N2H3COO)2.2H2O, zirconyl hydrazine carboxylate dihydrate, ZrO(N2H3COO)2.2H2O and their solid solution, ZrTiO2(N2H3COO)4.4H2O have been prepared for the first time and investigated as precursors to fine particle TiO2, ZrO2 and ZrTiO4 respectively. Titania(anatase) formed has a very high surface area of 110 m2/g and zirconium titanate showed very low dielectric loss (4 x 10(-4)).

Is tetramethyleneethane a ground state triplet?

We have examined a number of possible ways by which tetramethyleneethane (TME) can be a ground state triplet, as claimed by experimental studies, in violation of Ovchinnikov’s theorem for alternant hydrocarbons of equal bond lengths. Model exact π calculations of the low-lying states of TME, 3,4-dimethylenefuran and 3,4-dimethylenepyrrole were carried out using a diagrammatic valence bond approach. The calculations failed to yield a triplet ground state even after (a) tuning of electron correlation, (b) breaking alternancy symmetry, and (c) allowing for geometric distortions. In contrast to earlier studies of fine structure constants in other conjugated systems, the computedD andE values of all the low-lying triplet states of TME for various geometries are at least an order of magnitude different from the experimentally reported values. Incorporation of σ-π mixing by means of UHF MNDO calculations is found to favour a singlet ground state even further. A reinterpretation of the experimental results of TME is therefore suggested to resolve the conflict.

Microwave Irradiation Assisted Method for the Rapid Synthesis of fine Particles of alpha Al2O3 And alpha (Al1-XCrx)(2)O-3 And Their Coatings on Si(100)

Chromium substituted beta diketonate complexes of aluminium have been synthesized and employed as precursors for a novel soft chemistry process wherein microwave irradiation of a solution of the complex yields within minutes well crystallized needles of alpha (Al1 XCrx)(2)O-3 measuring 20 30 nm in diameter and 50 nm long By varying the microwave irradiation parameters and using a surfactant such as polyvinyl pyrrolidone the crystallite size and shape can be controlled and their agglomeration prevented These microstructural parameters as well as the polymorph of the Cr substituted Al2O3 formed may also be controlled by employing a different complex Samples of alpha (Al1 XCrx)(2)O-3 have been characterized by XRD FTIR and TEM The technique results in material of homogeneous metal composition, as shown by EDAX and can be adjusted as desired The technique has been extended to obtain coatings of alpha (Al1 XCrx)(2)O-3 on Si(100)

Tuning the electronic effective mass in double-doped SrTiO3

We elucidate the relationship between effective mass and carrier concentration in an oxide semiconductor controlled by a double-doping mechanism. In this model oxide system, Sr1-xLaxTiO3-delta, we can tune the effective mass ranging from 6 to 20m(e) as a function of filling (carrier concentration) and the scattering mechanism, which are dependent on the chosen lanthanum-and oxygen-vacancy concentrations. The effective mass values were calculated from the Boltzmann transport equation using the measured transport properties of thin films of Sr1-xLaxTiO3-delta. We show that the effective mass decreases with carrier concentration in this large-band-gap, low-mobility oxide, and this behavior is contrary to the traditional high-mobility, small-effective-mass semiconductors.

Porous, catalytically active palladium nanostructures by tuning nanoparticle interactions in an organic medium

We present a simple template-free method for the synthesis of interconnected hierarchical porous palladium nanostructures by controlling the aggregation of nanoparticles in organic media. The interaction between the nanoparticles is tuned by varying the dielectric constant of the medium consistent with DLVO calculations. The reaction products range from discrete nanoparticles to compact porous clusters with large specific surface areas. The nanoclusters exhibit hierarchical porosity and are found to exhibit excellent activity towards the reduction of 4-nitrophenol into 4-aminophenol and hydrogen oxidation. The method opens up possibilities for synthesizing porous clusters of other functional inorganics in organic media.

Microstructure evolution and hardness variation during annealing of equal channel angular pressed ultra-fine grained nickel subjected to 12 passes

The microstructure, thermal stability and hardness of ultra-fine grained (UFG) Ni produced by 12 passes of equal channel angular pressing (ECAP) through the route Bc were studied. Comparing the microstructure and hardness of the as-ECAPed samples with the published data on UFG Ni obtained after 8 passes of ECAP through the route Bc reveals a smaller average grain size (230 nm in the present case compared with 270 nm in 8-pass Ni), significantly lower dislocation density (1.08 x 10(14) m(-2) compared with 9 x 10(14) m(-2) in 8-pass Ni) and lower hardness (2 GPa compared with 2.45 GPa for 8-pass Ni). Study of the thermal stability of the 12-pass UFG Ni revealed that recovery is dominant in the temperature range 150-250A degrees C and recrystallisation occurred at temperatures > 250 A degrees C. The UFG microstructure is relatively stable up to about 400 A degrees C. Due to the lower dislocation density and consequently a lower stored energy, the recrystallisation of 12-pass ECAP Ni occurred at a higher temperature (similar to 250 A degrees C) compared with the 8-pass Ni (similar to 200 A degrees C). In the 12-pass Nickel, hardness variation shows that its dependence on grain size is inversely linear rather than the common grain size(-0.5) dependence.

Controlled combustion synthesis and properties of fine-particle NASICON materials

Fine-particle NASICON materials, Na1+xZr2P3-xSixO12 (where x = 0.0, 0.5, 1.0, 1.5, 2.0 and 2.5), have been prepared by controlled combustion of an aqueous solution containing stoicthiometric amounts of sodium nitrate, zirconyl nitrate, ammonium perchlorate, diammonium hydrogen phosphate, fumed silica and carbonohydrazide. Formation of NASICON has been confirmed by powder XRD, Si-29 NMR and IR spectroscopy. These NASICON powders are fine (average agglomerate size 5-12 mum) with a surface area varying from 8 to 30 m2 g-1. NASICON powders pelletized and sintered at 1100-1200-degrees-C for 5 h achieved 90-95% theoretical density and show fine-grain microstructure. The coefficient of thermal expansion of sintered NASICON compact was measured up to 500-degrees-C and changes f rom -3.4 x 10(-6) to 4.1 x 10(-6) K-1. The conductivity of Sintered Na3Zr2PSi2O12 compact at 300-degrees-C is 0.236 OMEGA-1 cm-1.

Synthesis and characterization of barium bis(citrato) oxozirconate(iv) tetrahydrate--A new molecular precursor for fine particle BaZrO3

Barium metazirconate (BaZrO3) fine powder has been produced by thermally decomposing a molecular precursor, barium bis(citrato)oxozirconate(IV) tetrahydrate at about 700-degrees-C. The precursor, Ba[ZrO(C6H6O7)2] . 4H2O (BZO) has been synthesized and characterized by employing a combination of spectroscopic and thermoanalytical techniques. The precursor undergoes thermal decomposition in three major stages: (i) dehydration to give an anhydrous barium zirconyl citrate, (ii) decomposition of the anhydrous citrate in a multistep process to form an ionic oxycarbonate intermediate, Ba2Zr2O5CO3, and (iii) decomposition of the oxycarbonate to produce BaZrO3 fine powder. The particle size of the resultant BaZrO3 is about 0.2 mum, and the surface area is found to be 4.0 m2 g-1.

Adaptive optimal tuning of a general class of stable LTI systems with restricted inputs

The problem addressed is one of model reference adaptive control (MRAC) of asymptotically stable plants of unknown order with zeros located anywhere in the s-plane except at the origin. The reference model is also asymptotically stable and lacking zero(s) at s = 0. The control law is to be specified only in terms of the inputs to and outputs of the plant and the reference model. For inputs from a class of functions that approach a non-zero constant, the problem is formulated in an optimal control framework. By successive refinements of the sub-optimal laws proposed here, two schemes are finally design-ed. These schemes are characterized by boundedness, convergence and optimality. Simplicity and total time-domain implementation are the additional striking features. Simulations to demonstrate the efficacy of the control schemes are presented.

Covariant differentials lead to the design of a novel self-tuning power system stabilizer

Application of differential geometry to study the dynamics of electrical machines by Gabriel Kron evoked only theoretical interest among the power system engineers and was considered hardly suitable for any practical use. Extension of Kron's work led to a physical understanding of the processes governing the small oscillation instability in power system. This in turn has made it possible to design a self-tuning Power System Stabilizer to contain the oscillatory instability over arm extended range of system and operating conditions. This paper briefly recounts the history of this development and touches upon the essential design features of the stabilizer. It presents some results from simulation studies, laboratory experiments and recently conducted field trials at actual plants-all of which help to establish the efficacy of the proposed stabilizer and corroborate the theoretical findings.

Photocatalysis on Fine Powders of Perovskite Oxides

Fine powders of semiconductor oxides have been widely used as photocatalysts for many reactions. Among the various photocatalytic reactions, water splitting has been given much importance, since it is a promising chemical route for solar energy conversion. Perovskite oxides, in particular SrTiO, have been commonly used as photocatalysts because some of them can decompose H,O into H, and 0, without an external bias potential (1). In turn, this is because the conduction band (CB) edges of some of the perovskite oxides are more negative than the H+/H, energy level. Since the catalytic activity is related to the surface properties of the solids, fine powders rather than single crystals are used. Photocatalysis on fine powers can be conveniently discussed in three parts, viz. preparation, characterization and their catalytic activity. Presently, photo-decomposition of water using SrTiO, fine powders is discussed in greater detail, although other photocatalytic reactions on various perovskite oxides are also briefly dealt with.

Characteristic water contents of a fine-grained soil-water system

This paper critically appraises the limitations of the liquid-limit water content of clayey soils determined conventionally either by percussion cup or by the cone penetration method. It is shown that the conventional liquid limit and plastic limit are arbitrary, strength-based water contents and that they cannot represent the plasticity limits, and that the state of the soil-water system at the conventional liquid limit does not correspond to a stress-free reference state. The present investigation identifies three characteristic limiting water contents for a soil-water system which have well-defined, unique mechanisms controlling them, namely the free swell limit, settling limit and shrinkage limit. Simple procedures for the determination of the free swell limit and settling limit of natural soils are presented. The settling limit is shown to be the 'real liquid limit' of any clayey soil. With a number of experimental illustrations, it is clearly shown that the settling limit represents the maximum water-holding capacity of clayey soils and that it corresponds to the stress-free reference state.