Thermal degradation processes in polysulfide copolymers investigated by direct pyrolysis mass spectrometry and flash pyrolysis-gas chromatography/mass spectrometry

This is the first report on the analysis of random block polysulfide copolymers containing different amounts of repeating units in the copolymer backbone, which has been studied by direct pyrolysis mass spectrometry (DPMS) and by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The homopolymers such as poly(ethylene sulfide) (PES), poly(styrene sulfide) (PSS), and two random copolymers, viz., poly(ethylene sulfide(x)-co-styrene sulfide(y)) [copolymer I (x = y = 0.5) and copolymer II (x = 0.74, y = 0.26)] were investigated by both DPMS and Py-GC/MS (except copolymer II) techniques. In the case of copolymer I, the thermal degradation products of SE1, SE2, S-2, and S2E (S = styrene sulfide, E = ethylene sulfide) were detected in DPMS, whereas the formation of SE1 and SE2 were observed by Py-GC/MS technique. However, for copolymer II, SE3 was also found along with SE1, SE2, S-2, and S2E in DPMS. The formation of additional product (SE3) observed in copolymer II could be due to an increase in the block length formed during copolymerization. Further, a comparative study on thermal degradation of PES, poly(ethylene disulfide) (PEDS), and poly(ethylene tetrasulfide) (PETS) were investigated by Py-GC/MS. The pyrolysis products detected by both DPMS and Py-GC/MS indicates that the thermal decomposition of these polymers yield cyclic sulfides through an intramolecular exchange or by backbiting processes. The linear products with thiol and vinyl groups were also observed by Py-GC/MS along with the cyclic products via carbon hydrogen transfer reaction.

An economical method for direct numerical simulation studies of transitional round jets

A pseudo-spectral method based on Fourier expansions in a Cartesian coordinate system is shown to be an economical method for direct numerical simulation studies of transitional round jets, Several characteristics of the solutions are presented to establish the validity of the solutions in spite of the unnatural choices. We show that neither periodicity, nor the use of a Cartesian system have adversely affected the simulations, Instead, there are benefits in terms of ease of computing and lack of the usual restrictions due to grid structure near the jet axis. By computing the simultaneous evolution of passive scalers, the process of reaction in round jet burners, between a fuel-laden jet and an ambient oxidizer, was also simulated. Some typical solutions are shown and then the results of analysis of these data are summarized. (C) 2001 Elsevier Science Ltd, All rights reserved.

Direct measurement of phase of foreward-scattered light using polarization heterodyne interferometer

We describe direct measurement of phase of ballistic photons transmitted through objects hidden in a turbid medium using a polarization interferometer employing a rotating analyzer. The unwrapped phase difference measurements from interferometry was possible for medium levels of turbidity and accurate phase measurement from the sinusoidal intensity was not detectable when l/l* is increased beyond 4.3. The measured phase on reconstruction using standard tomographic algorithms resulted in the recovery of the refractive index profile of the object hidden in the turbid medium.

Direct numerical simulation of turbulent spots

A group of high-order finite-difference schemes for incompressible flow was implemented to simulate the evolution of turbulent spots in channel flows. The long-time accuracy of these schemes was tested by comparing the evolution of small disturbances to a plane channel flow against the growth rate predicted by linear theory. When the perturbation is the unstable eigenfunction at a Reynolds number of 7500, the solution grows only if there are a comparatively large number of (equispaced) grid points across the channel. Fifth-order upwind biasing of convection terms is found to be worse than second-order central differencing. But, for a decaying mode at a Reynolds number of 1000, about a fourth of the points suffice to obtain the correct decay rate. We show that this is due to the comparatively high gradients in the unstable eigenfunction near the walls. So, high-wave-number dissipation of the high-order upwind biasing degrades the solution especially. But for a well-resolved calculation, the weak dissipation does not degrade solutions even over the very long times (O(100)) computed in these tests. Some new solutions of spot evolution in Couette flows with pressure gradients are presented. The approach to self-similarity at long times can be seen readily in contour plots.

A self-supported 40W direct methanol fuel cell system

A self-supported 40W Direct Methanol Fuel Cell (DMFC) system has been developed and performance tested. The auxiliaries in the DMFC system comprise a methanol sensor, a liquid-level indicator, and fuel and air pumps that consume a total power of about 5W. The system has a 15-cell DMFC stack with active electrode-area of 45 cm(2). The self-supported DMFC system addresses issues related to water recovery from the cathode exhaust, and maintains a constant methanol-feed concentration with thermal management in the system. Pure methanol and water from cathode exhaust are pumped to the methanol-mixing tank where the liquid level is monitored and controlled with the help of a liquid-level indicator. During the operation, methanol concentration in the feed solution at the stack outlet is monitored using a methanol sensor, and pure methanol is added to restore the desired methanol concentration in the feed tank by adding the product water from the cathode exhaust. The feed-rate requirements of fuel and oxidant are designed for the stack capacity of 40W. The self-supported DMFC system is ideally suited for various defense and civil applications and, in particular, for charging the storage batteries.

Direct mdct domain psychoacoustic modeling

We extend the recently proposed spectral integration based psychoacoustic model for sinusoidal distortions to the MDCT domain. The estimated masking threshold additionally depends on the sub-band spectral flatness measure of the signal which accounts for the non- sinusoidal distortion introduced by masking. The expressions for masking threshold are derived and the validity of the proposed model is established through perceptual transparency test of audio clips. Test results indicate that we do achieve transparent quality reconstruction with the new model. Performance of the model is compared with MPEG psychoacoustic models with respect to the estimated perceptual entropy (PE). The results show that the proposed model predicts a lower PE than other models.

Direct Infrared Absorption Spectroscopy of Benzene Dimer

The direct infrared (IR) absorption spectrum of benzene dimer formed in a free-jet expansion was recorded in the 3.3 mu m region for the first time. This has led to the observation of the C H stretching fundamental mode nu(13) (B(1u)), which is both IR and Raman forbidden in the monomer. Moreover, the IR forbidden and Raman allowed nu(7) (E(2g)) mode has been observed as well. These two modes were found to be red-shifted along with the IR allowed nu(20) (E(1u)) mode, as previously reported by Erlekam et al. [Erlekam; Frankowski; Meijer; Gert von Helden J. Chem. Phys. 2006, 124, 171101], using ion-dip spectroscopy, contrary to the blue-shift predicted earlier by theoretical studies. The observation of the nu(13) band indicates that the symmetry is reduced in the dimer, confirming the T-shaped structure observed by Erlekam et al. Our experimental results have not provided any direct evidence for the presence of the parallel displaced geometry, the main objective of the present work, as predicted by theoretical calculations.

Bio-Composite Membrane Electrolytes for Direct Methanol Fuel Cells

A new class of bio-composite polymer electrolyte membranes comprising chitosan (CS) and certain biomolecules in particular, plant hormones such as 3-indole acetic acid (IAA), 4-chlorophenoxy acetic acid (CAA) and 1-naphthalene acetic acid (NAA) are explored to realize proton-conducting bio-composite membranes for application in direct methanol fuel cells (DMFCs). The sorption capability, proton conductivity and ion-exchange capacity of the membranes are characterized in conjunction with their thermal and mechanical behaviour. A novel approach to measure the permeability of the membranes to both water and methanol is also reported, employing NMR imaging and volume localized NMR spectroscopy, using a two compartment permeability cell. A DMFC using CS-IAA composite membrane, operating with 2M aqueous methanol and air at 70 degrees C delivers a peak power density of 25 mW/cm(2) at a load current density of 150 mA/cm(2). The study opens up the use of bio-compatible membranes in polymer-electrolyte-membrane fuel cells. (C) 2011 The Electrochemical Society. [DOI: 10.1149/2.030111jes] All rights reserved.