Direct and sensitized (energy and electron transfer) geometric isomerization of stilbene within zeolites: a comparison between solution and zeolite as reaction media

The trans- and cis-stilbenes upon inclusion in NaY zeolite are thermally stable. Direct excitation and triplet sensitization results in geometric isomerization and the excited state behavior under these conditions are similar to that in solution. Upon direct excitation, a photostationary state consisting of 65% cis and 35% trans isomers is established. Triplet sensitization with 2-acetonaphthone gave a photostationary state consisting of 63% cis and 37% trans isomers. These numbers are similar to the ones obtained in solution. Thus, the presence of cations and the confined space within the zeolite have very little influence on the overall chemistry during direct and triplet sensitization. However, upon electron transfer sensitization with N-methylacridinium (NMA) as the sensitizer within NaY, isomerization from cis-stilbene radical cation to trans-stilbene occurs and the recombination of radical ions results in triplet stilbene. Prolonged irradiation gave a photostationary state (65% cis and 35% trans) similar to triplet sensitization. This behavior is unique to the zeolite and does not take place in solution. Steady state fluorescence measurements showed that the majority of stilbene molecules are close to the N-methylacridinium sensitizer. Diffuse reflectance flash photolysis studies established that independent of the isomer being sensitized only trans radical cation is formed. Triplet stilbene is believed to be generated via recombination of stilbene radical cation and sensitizer radical anion. One should be careful in using acidic HY zeolite as a medium for photoisomerization of stilbenes. In our hands, in these acidic zeolites isomerization dominated the photoisomerization. (C) 2002 Elsevier Science B.V. All rights reserved.

Low-pressure MOCVD of Al2O3 films using aluminium acetylacetonate as precursor: nucleation and growth

A study of the deposition of aluminium oxide films by low-pressure metalorganic chemical vapour deposition from the complex aluminium acetylacetonate, in the absence of an oxidant gas, has been carried out. Depositions on to Si(100), stainless steel, and TiN-coated cemented carbide are found to be smooth, shiny, and blackish. SIMS, XPS and TEM analyses reveal that films deposited at temperatures as low as 600 degreesC contain small crystallites Of kappa-Al2O3, embedded in an amorphous matrix rich in graphitic carbon. Optical and scanning electron microscopy reveal a surface morphology made up of spherulites that suggests that film growth might involve a melting process. A nucleation and growth mechanism, involving the congruent melting clusters of precursor molecules on the hot substrate surface, is therefore invoked to explain these observations. An effort has been made experimentally to verify this proposed mechanism. (C) 2002 Elsevier Science B.V. All rights reserved.

MOCVD of aluminium oxide films using aluminiurn beta-diketonates as precursors

Deposition of Al2O3 coatings by CVD is of importance because they are often used as abrading material in cemented carbide cutting tools. The conventionally used CVD process for Al2O3 involves the corrosive reactant AlCl3. In this paper, we report on the thermal characterisation of the metalorganic precursors namely aluminium tristetramethyl-heptanedionate [Al(thd)(3)] and aluminium tris-acetylacetonate [Al(acac)(3)] and their application to the CVD of Al2O3 films. Crystalline Al2O3 films were deposited by MOCVD at low temperatures by the pyrolysis of Al(thd)(3) and Al(acac)(3). The films were deposited on a TiN-coated tungsten carbide (TiN/WC) and Si(100) substrates in the temperature range 500-1100degreesC. The as-deposited films were characterised by x-ray diffraction, optical microscopy, scanning and transmission electron microscopy, Auger electron spectroscopy. The observed crystallinity of films grown at low temperatures, their microstructure, and composition may be interpreted in terms of a growth process that involves the melting of the metalorganic precursor on the hot growth surface.

Noise and outlier removal from jet engine health signals using weighted FIR median hybrid filters

The removal of noise and outliers from measurement signals is a major problem in jet engine health monitoring. Topical measurement signals found in most jet engines include low rotor speed, high rotor speed. fuel flow and exhaust gas temperature. Deviations in these measurements from a baseline 'good' engine are often called measurement deltas and the health signals used for fault detection, isolation, trending and data mining. Linear filters such as the FIR moving average filter and IIR exponential average filter are used in the industry to remove noise and outliers from the jet engine measurement deltas. However, the use of linear filters can lead to loss of critical features in the signal that can contain information about maintenance and repair events that could be used by fault isolation algorithms to determine engine condition or by data mining algorithms to learn valuable patterns in the data, Non-linear filters such as the median and weighted median hybrid filters offer the opportunity to remove noise and gross outliers from signals while preserving features. In this study. a comparison of traditional linear filters popular in the jet engine industry is made with the median filter and the subfilter weighted FIR median hybrid (SWFMH) filter. Results using simulated data with implanted faults shows that the SWFMH filter results in a noise reduction of over 60 per cent compared to only 20 per cent for FIR filters and 30 per cent for IIR filters. Preprocessing jet engine health signals using the SWFMH filter would greatly improve the accuracy of diagnostic systems. (C) 2002 Published by Elsevier Science Ltd.

Studies on a new high-intensity low-emission burner

This paper presents computational and experimental results on a new burner configuration with a mild combustion concept with heat release rates up to 10 MW/m(3). The burner configuration is shown to achieve mild combustion by using air at ambient temperature at high recirculation rates (similar to250%-290%) both experimentally and computationally. The principal features of the configuration are: (1) a burner with forward exit for exhaust gases; (2) injection of gaseous fuel and air as multiple, alternate, peripheral highspeed jets at the bottom at ambient temperature, thus creating high enough recirculation rates of the hot combustion products into fresh incoming reactants; and (3) use of a suitable geometric artifice-a frustum of a cone to help recirculation. The computational studies have been used to reveal the details of the flow and to optimize the combustor geometry based on recirculation rates. Measures, involving root mean square temperature fluctuations, distribution of temperature and oxidizer concentration inside the proposed burner, and a classical turbulent diffusion jet flame, are used to distinguish between them quantitatively. The system, operated at heat release rates of 2 to 10 MW/m(3) (compared to 0.02 to 0.32 MW/m(3) in the earlier studies), shows a 10-15 dB reduction in noise in the mild combustion mode compared to a simple open-top burner and exhaust NOx emission below 10 ppm for a 3 kW burner with 10% excess air. The peak temperature is measured around 1750 K, approximately 300 K lower than the peak temperature in a conventional burner.

Electron beam surface melting of model 1200 Al alloys

Electron beam surface melting has been used to characterise the phase content formed in a number of model 1200 series Al alloys with increasing solidification velocity in the range 2–50 mm s−1, typical of that experienced during continuous strip casting. Phases were extracted from the Al matrix and analysed by X-ray diffraction. A qualitative solidification microstructure selection map has been produced, showing that, for a given Fe content of 0.55 wt.%: with increasing solidification velocity the metastable aluminides FeAl6 and FeAlm displace equilibrium Fe4Al13 at Si contents 0.15 wt.%, and that α-AlFeSi is an equilibrium phase at a Si content ≥0.50 wt.%.

High contrast imaging and thickness determination of graphene with in-column secondary electron microscopy

We report a new method for quantitative estimation of graphene layer thicknesses using high contrast imaging of graphene films on insulating substrates with a scanning electron microscope. By detecting the attenuation of secondary electrons emitted from the substrate with an in-column low-energy electron detector, we have achieved very high thickness-dependent contrast that allows quantitative estimation of thickness up to several graphene layers. The nanometer scale spatial resolution of the electron micrographs also allows a simple structural characterization scheme for graphene, which has been applied to identify faults, wrinkles, voids, and patches of multilayer growth in large-area chemical vapor deposited graphene. We have discussed the factors, such as differential surface charging and electron beam induced current, that affect the contrast of graphene images in detail. (C) 2011 American Institute of Physics. doi:10.1063/1.3608062]

Turbulence measurements in an ‘equilibrium’ axisymmetric wall jet Journal

This paper reports measurements of turbulent quantities in an axisymmetric wall jet subjected to an adverse pressure gradient in a conical diffuser, in such a way that a suitably defined pressure-gradient parameter is everywhere small. Self-similarity is observed in the mean velocity profile, as well as the profiles of many turbulent quantities at sufficiently large distances from the injection slot. Autocorrelation measurements indicate that, in the region of turbulent production, the time scale of ν fluctuations is very much smaller than the time scale of u fluctuations. Based on the data on these time scales, a possible model is proposed for the Reynolds stress. One-dimensional energy spectra are obtained for the u, v and w components at several points in the wall jet. It is found that self-similarity is exhibited by the one-dimensional wavenumber spectrum of $\overline{q^2}(=\overline{u^2}+\overline{v^2}+\overline{w^2})$, if the half-width of the wall jet and the local mean velocity are used for forming the non-dimensional wavenumber. Both the autocorrelation curves and the spectra indicate the existence of periodicity in the flow. The rate of dissipation of turbulent energy is estimated from the $\overline{q^2}$ spectra, using a slightly modified version of a previously suggested method.

Transmission electron microscopy study of domain structures in ferroelectric SrBi2Nb2O9 ceramics

A transmission electron microscopy study has been carried out on the domain structures of SrBi2Nb2O9 (SBN) ferroelectric ceramics which belong to the Aurivillius family of bismuth layered perovskite oxides. SBN is a potential candidate for Ferroelectric Random access memory (FeRAM) applications. The 90° ferroelectric domains and antiphase boundaries (APBs) were identified with dark field imaging techniques using different superlattice reflections which arise as a consequence of octahedral rotations and cationic shifts. The 90° domain walls are irregular in shape without any faceting. The antiphase boundaries are less dense compared to that of SrBi2Ta2O9(SBT). The electron microscopy observations are correlated with the polarization fatigue nature of the ceramic where the domain structures possibly play a key role in the fatigue- free behavior of the Aurivillius family of ferroelectric oxides.

Electron Cyclotron Resonance in Strained Si and Si0.94Ge0.06 Channels on Relaxed Si0.62Ge0.38 Buffers Grown by Rapid Thermal Chemical Vapor Deposition

We report the far-infrared measurements of the electron cyclotron resonance absorption in n-type Si/Si0. 62Ge0.38 and Si0.94Ge0.06 /Si0. 62Ge0.38 modulation- doped heterostructures grown by rapid thermal chemical vapor deposition. The strained Si and Si0.94Ge0.06 channels were grown on relaxed Si0.62Ge0.38 buffer layers, which consist of 0.6 μm uniform Si0.62Ge0.38 layers and 0.5 μm compositionally graded relaxed SiGe layers from 0% Ge to 38 % Ge. The buffer layers were annealed at 800 °C for 1 hr to obtain complete relaxation. The samples had 100 Å spacers and 300 Å 2×1019 cm-3 n-type supply layers on the tops of the 75 Å channels. The far-infrared measurements of electron cyclotron resonance were performed at 4K with the magnetic field of 4 – 8 Tesla. The effective masses determined from the slope of center frequency of absorption peak vs applied magnetic field plot are 0.20 mo and 0.19 mo for the two dimensional electron gases in the Si and Si0.94Ge0.06 channels, respectively. The Si effective mass is very close to that of two dimensional electron gas in Si MOSFET (0.198mo). The electron effective mass of Si0.94Ge0.06 is reported for the first time and about 5 % lower than that of pure Si.

Microstructure and mechanical properties of electron beam weld joints of a Zr41Ti14Cu12Ni10Be23 bulk metallic glass with Zr

The electron beam welding technique was used to join Zr41Ti14Cu12Ni10Be23 bulk metallic glass (BMG) to crystalline pure Zr. Compositional, microstructural, and mechanical property variations across the welded interface were evaluated. It is shown that a crystalline layer develops close to the welding interface. Transmission electron microscopy of this layer indicates the crystalline phase to be tetragonal with lattice parameters close to that reported for Zr2Ni. However, the composition of this phase is different as it contains other alloying additions. The interface layer close to the bulk metallic glass side contains nanocrystalline Zr2Cu phase embedded in the glassy matrix. Nanoindentation experiments indicate that the hardness of the crystalline layer, although less than the bulk metallic glass, is more than the Zr itself. Commensurately, tensile tests indicate that the failure of the welded samples occurs at the Zr side rather than at the weld joint.

Heat shock protein 70 as a biomarker of heat stress in a simulated hot cockpit

Background: Fighter pilots are frequently exposed to high temperatures during high-speed low-level flight. Heat strain can result in temporary impairment of cognitive functions and when severe, loss of consciousness and consequent loss of life and equipment. Induction of stress proteins is a highly conserved stress response mechanism from bacteria to humans. induced stress protein levels are known to be cytoprotective and have been correlated with stress tolerance. Although many studies on the heat shock response mechanisms have been performed in cell culture and animal model systems, there is very limited information on stress protein induction in human subjects. Hypothesis: Heat shock proteins (Hsp), especially Hsp70, may be induced in human subjects exposed to high temperatures in a hot cockpit designed to simulate heat stress experienced in low flying sorties. Methods: Six healthy volunteers were subjected to heat stress at 55degreesC in a high temperature cockpit simulator for a period of 1 h at 30% humidity. Physiological parameters such as oral and skin temperatures, heart rate, and sweat rate were monitored regularly during this time. The level of Hsp70 in leukocytes was examined before and after the heat exposure in each subject. Conclusions: Hsp70 was found to be significantly induced in all the six subjects exposed to heat stress. The level of induced Hsp70 appears to correlate with other strain indicators such as accumulative circulatory strain and Craig's modified index. The usefulness of Hsp70 as a molecular marker of heat stress in humans is discussed.

Influence of homogenization on the processing map for hot working of as-cast Mg-2Zn-1Mn alloy

Processing maps have been developed for hot deformation of Mg-2Zn-1Mn alloy in as-cast condition and after homogenization with a view to evaluate the influence of homogenization. Hot compression data in the temperature range 300-500degreesC and strain rate range 0.001-100 s(-1) were used for generating the processing map. In the map for the as-cast alloy the domain of dynamic recrystallization occurring, at 450degreesC and 0.1 s(-1) has merged with another domain occurring at 500degreesC and 0.001 s(-1) representing grain boundary cracking. The latter domain is eliminated by homogenization and the dynamic recrystallization domain expanded with a higher peak efficiency occurring at 500 degreesC and 0.05 s(-1). The flow localization occurring at strain rates higher than 5 s(-1) is unaffected by homogenization.