Investigations of the reduction behavior of Iron-impregnated alumina gels (Fe/AlOOH) and the formation of Fe0-Al2O3 metal-ceramic composites

Fe/AlOOH gels calcined and reduced at different temperatures have been investigated by a combined use of Mossbauer spectroscopy, x-ray diffraction, and electron microscopy in order to obtain information on the nature of the iron species formed as well as the various reduction processes. Calcination at or below 1070 K mainly gives reducible Fe3+ while calcination at higher temperatures gives substitutional Fe3+ in the form of Al2-xFexO3. The Fe3+ species in the calcined samples are, by and large, present in the form of small superparamagnetic particles. Crystallization of Al2O3 from the gels is catalyzed by Fe2O3 as well as FeAl2O4. Fe (20 wt. %)/AlOOH gels calcined at or below 870 K give FeAl2O4 when reduced in hydrogen at 1070 K or lower and a ferromagnetic Fe0-Al2O3 composite (with the metallic Fe particles >100 angstrom) when reduced at 1270 K. Samples calcined at 1220 K or higher give the Fe0-Al2O3 composite when reduced in the 870-12,70 K range, but a substantial proportion of Fe3+ remains unreduced in the form of Al2-xFexO3, showing thereby the extraordinary stability of substitutional Fe3+ to reduction even at high temperatures. Besides the ferromagnetic Fe0-Al2O3 composite, high-temperature reduction of Al2-xFexO3 yields a small proportion of superparamagnetic Fe0-Al2O3 wherein small metallic particles (<100 angstrom) are embedded in the ceramic matrix. In order to preferentially obtain the Fe0-Al2O3 composite on reduction, Fe/AlOOH gels should be calcined at low temperatures (less-than-or-equal-to 1100 K); high-temperature calcination results in Al2-xFexO3. Several modes of formation of FeAl2O4 are found possible during reduction of the gels, but a novel one is that involving the reaction, 2Fe3+ + Fe0 --> 3Fe2+.

A facile route to synthesize silver nanoparticles in polyelectrolyte capsules

We are reporting a novel green approach to incorporate silver nanoparticles (NPs) selectively in the polyelectrolyte capsule shell for remote opening of polyelectrolyte capsules. This approach involves in situ reduction of silver nitrate to silver NPs using PEG as a reducing agent (polyol reduction method). These nanostructured capsules were prepared via layer by layer (LbL) assembly of poly(allylamine hydrochloride) (PAH) and dextran sulfate (DS) on silica template followed by the synthesis of silver NPs and subsequently the dissolution of the silica core. The size of silver nanoparticles synthesized was 60 +/- 20 nm which increased to 100 +/- 20 nm when the concentration of AgNO3 increased from 25 mM to 50 mM. The incorporated silver NPs induced rupture and deformation of the capsules under laser irradiation. This method has advantages over other conventional methods involving chemical agents that are associated with cytotoxicity in biological applications such as drug delivery and catalysis. (C) 2011 Elsevier B.V. All rights reserved.

High swirl-inducing piston bowls in small diesel engines for emission reduction

Detailed three-dimensional CFD simulations involving flow and combustion chemistry are used to study the effect of swirl induced by re-entrant piston bowl geometries on pollutant emissions from a single-cylinder diesel engine. The baseline engine configuration consists of a hemispherical piston bowl and an injector with finite sac volume. The first iteration involved using a torroidal, slightly re-entrant bowl geometry, and a sac-less injector. Pollutant emission measurements indicated a reduction in emissions with this modification. Simulations on both configurations were then conducted to understand the effect of the changes. The simulation results indicate that the selected piston bowl geometry could actually be reducing the in-cylinder swirl and turbulence and the emission reduction may be entirely due to the introduction of the sac-less injector. In-cylinder air motion was then studied in a number of combustion chamber geometries, and a geometry which produced the highest in-cylinder swirl and Turbulence Kinetic Energy (TKE) around the compression top dead centre (TDC) was identified. The optimal nature of this re-entrant piston bowl geometry is confirmed by detailed combustion simulations and emission predictions. (C) 2010 Elsevier Ltd. All rights reserved.

Novel reduction (Zn-AcOH) of DDHQ esters - A new route to tropone synthesis

Zn/acetic acid reaction of DDHQ esters 1 a-d gave the saturated acids 3 a-d and the hydrocarbons 7 a-d. The intermediacy of the aldehydes 10 and 11 in the formation of the products has been established. Oxidation of hydrocarbons 7a and 7b gave the corresponding tropones (5a and 5b).

Crystal growth and defects characterization of zinc tris (thiourea) sulfate: a novel metalorganic nonlinear optical crystal

Single crystals of the metalorganic nonlinear optical material zinc tris (thiourea) sulfate (ZTS) were grown from aqueous solution. The morphology of the crystals was indexed. The grown crystals were characterized by recording the powder X-ray diffraction pattern and by identifying the diffracting planes. Spectrophotometric studies on ZTS reveal that it has good transparency for the Nd: YAG laser fundamental wavelength. Differential thermal analysis of ZTS indicates that the material does not sublime before melting but decomposes immediately after melting. The defect content of the crystals was estimated using etching and X-ray topography. The mechanical hardness anisotropy was evaluated in the (100) plane, which indicates the presence of soft directions.

Reduction of quinolines to 1,2,3,4-tetrahydro derivatives employing a combination of NaCNBH3 and BF3.OEt(2)

A regiospecific reduction of quinolines (and 1,10-phenanthroline) into the corresponding 1,2,3,4-tetrahydro derivatives using a combination of sodium cyanoborohydride and boron trifluoride etherate in refluxing methanol is described. Under the same conditions indole and acridine reduced to the corresponding dihydroderivatives, whereas acyl group transfer from oxygen to nitrogen atom is also noticed in the case of 8-acyloxyquinolines.

Reduction of DDHQ and TCC esters by NaBH4-its specificity in the presence of Alkyl/Aryl esters

DDHQ/TCC esters 3a–f, 7a–g were prepared either by oxidation of spiroketones 1 with DDQ/Image -chloranil or by condensation of acid chloride with DDHQ/TCC. NaBH4 reduction of unsaturated DDHQ 3a–b and TCC 7a–c esters gave the corresponding allylic alcohols in good yield without any observable 1,4-addition products. Reduction of saturated esters 3e, 7d, gave the corresponding alcohols. Alkyl esters 5 and 6, methyl benzoate and phenyl benzoate remained unaffected under these reduction conditions. In the reduction of compound 7e containing both alkyl and TCC esters, TCC ester is selectively reduced. Reduction of TCC mono esters 7f–g gave the lactones. The observed facile reduction has been rationalised.

Use of finite wordlength FIR digital filter structures with improved magnitude and phase characteristics for reduction of muscle noise in EEG signals

One of the main disturbances in EEG signals is EMG artefacts generated by muscle movements. In the paper, the use of a linear phase FIR digital low-pass filter with finite wordlength precision coefficients is proposed, designed using the compensation procedure, to minimise EMG artefacts in contaminated EEG signals. To make the filtering more effective, different structures are used, i.e. cascading, twicing and sharpening (apart from simple low-pass filtering) of the designed FIR filter Modifications are proposed to twicing and sharpening structures to regain the linear phase characteristics that are lost in conventional twicing and sharpening operations. The efficacy of all these transformed filters in minimising EMG artefacts is studied, using SNR improvements as a performance measure for simulated signals. Time plots of the signals are also compared. Studies show that the modified sharpening structure is superior in performance to all other proposed methods. These algorithms have also been applied to real or recorded EMG-contaminated EEG signal. Comparison of time plots, and also the output SNR, show that the proposed modified sharpened structure works better in minimising EMG artefacts compared with other methods considered.

Reduction of electric arc furnace slags in stainless steelmaking - Part 2 Mechanism of CrOx reduction

The mechanism of reduction of iron and chromium oxide from synthetic electric are furnace stainless steelmaking slags has been studied. The activation energy for reduction of FeO depends on the FeO content of the slag and the nature of the product formed. The rate of reduction of both FeO and Cr2O3 is controlled by diffusion of ions in the slag phase. The reduction of Cr2O3 primarily takes place at the slag/Fe-C droplets interface. IS/1352b. (C) 1998 The Institute of Materials.

Reduction of electric are furnace slags in stainless steelmaking - Part 1 Observations

Simultaneous reduction of iron and chromium oxides from synthetic electric are furnace stainless steelmaking slag in a graphite crucible has been studied. Above the melting point of iron the reduction of iron oxide leads to a carbon saturated Fe-C melt, but below the melting point of iron initially solid iron or iron carbide forms on the crucible surface. Only when a certain number of Fe-C droplets are formed does the reduction of chromium oxide start to form an Fe-Cr-C alloy. The reaction proceeds with pronounced foaming which depends on the basicity, temperature, and iron oxide content of the slag. IS/1352a (C) 1998 The Institute of Materials.

Laboratory studies on the volume change characteristics of kaolinite contaminated with sodium phosphate/sulfate

Reported distress to an industrial structure from phosphate/sulfate contamination of kaolinitic foundation soil at an industrial location in Southern India prompted this laboratory study. The study examines the short-term effect of sodium sulfate/phosphate contamination on the swell/compression characteristics of a commercial kaolinite. Experimental results showed that the unsaturated contaminated kaolinite specimens exhibited slightly higher swell potentials and lower compressions than the unsaturated uncontaminated kaolinite specimens. It is suggested that the larger double layer promoted by the increased exchangeable sodium ion concentration is responsible for the slightly higher swell potentials and lower compressions of the unsaturated contaminated kaolinite specimens.

Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecane-8,11-dione

NaBH4 reduction of a cage dione proceeds in a stereospecific fashion to give the endo,endo-diol. This reactivity is related to the crystal structure.

Synthesis of Ti, Ga, and V nitrides: Microwave-assisted carbothermal reduction and nitridation

A simple, novel, and fast method of preparation of metal nitride powders (GaN, TiN, and VN) using microwave-assisted carbothermal reduction and nitridation has been demonstrated. The procedure uses the respective oxides and amorphous carbon powder as the starting materials. Ammonia gas is found to be more effective in nitridation than high-purity N-2 gas. Complete nitridation is achieved by the use of a slight excess of amorphous carbon. Metals themselves are not found to be effectively nitrided. The products were characterized using XRD, TEM, and SAED and found to possess good crystallinity and phase purity. The method can be of general applicability for the preparation of metal nitrides.