Thermal Cycling Stability of Silica Membranes for Gas Separation

Hydrogen is being seen as an alternative energy carrier to conventional hydrocarbons to reduce greenhouse gas emissions. High efficiency separation technologies to remove hydrogen from the greenhouse gas, carbon dioxide, are therefore in growing demand. Traditional thermodynamic separation systems utilise distillation, absorption and adsorption, but are limited in efficiency at compact scales. Molecular sieve silica (MSS) membranes can perform this separation as they have high permselectivity of hydrogen to carbon dioxide, but their stability under thermal cycling is not well reported. In this work we exposed a standard MSS membrane and a carbonised template MSS (CTMSS) membrane to thermal cycling from 100 to 450°C. The standard MSS and carbonised template CTMSS membranes both showed permselectivity of helium to nitrogen dropping from around 10 to 6 in the first set of cycles, remaining stable until the last test. The permselectivity drop was due to small micropore collapse, which occurred via structure movement during cycling. Simulating single stage membrane separation with a 50:50 molar feed of H2:CO2, H2 exiting the permeate stream would start at 79% and stabilise at 67%. Higher selectivity membranes showed less of a purity drop, indicating the margin at which to design a stable membrane separation unit for CO2 capture.

Molecular Sieve Silica (MSS) Membranes for Gas Separation and Reaction Processes

Weakly branched silica films formed by the two-step sol-gel process allow for the formation of high selectivity membranes for gas separation. 29Si NMR and gas permeation showed that reduced crosslinking leads to He/CH4 selectivity improvement from 300 to 1000. Applied in membrane reactor for cyclohexane conversion to benzene, conversions were achieved at 14 fold higher than a conventional reactor at 250°C. Hydrothermal stability studies showed that carbon templating of silica is required for hydrothermally stable membranes. From our work it was shown that with correct application of chemistry, practical membrane systems can be built to suit gas separation (e. g. hydrogen fuel) and reactor systems.

Hydrothermal stable templated molecular sieve silica (TMSS) membranes for gas separation

In this work we compare the hydrothermal stability performance of a Templated Molecular Sieve Silica (TMSS) membrane against a standard, non-templated Molecular Sieve Silica (MSS) membrane. The tests were carried under dry and wet (steam) conditions for single gas (He, H2, CO and CO2) at 1-2 atm membrane pressure drop at 200oC. Single gas TMSS membrane H2, permeance and H2/CO permselectivity was found to be 2.05 x 10-8 mols.m-2.s-1.Pa-1 and 15, respectively. The MSS membrane showed similar selectivity, but increased overall flux. He permeance through membranes decayed at a rate of 4-5 x 10-10 mols.m-2.s-1.Pa-1 per day regardless of membrane ambience (dry or wet). Although H2/CO permselectivity of the TMSS membrane slightly improved from 15 to 18 after steam testing, the MSS membrane resulted in significant reduction from 16 to 8.3. In addition, membrane regeneration after more than 50 days resulted in the TMSS membrane reverting to its original permeation levels while no significant improvements were observed for the MSS membra ne. Results showed that the TMSS membrane had enhanced hydrothermal stability and regeneration ability.

Hydrothermal Stability of Modified Silica Membranes for Gas Separation

A new class of hybrid molecular sieve silica (MSS) membranes is developed and tested against standard and organic templated membranes. The hybrid membrane is synthesized by the standard sol-gel process, integrating a template (methyltriethoxysilane - MTES) and a C6 surfactant (triethylhexylammonium bromide) into the silica film matrix. After hydro treatment under a relative humidity of 96% for 50h, the hybrid membrane shows no changes in its gas separation capabilities or energy of mobility. The structural characteristics and integrity of the hybrid membrane are retained due to a high concentration of organophilic functional groups and alkoxides observed using 29 Si NMR. In contrast, the structural integrity of the membranes prepared with non-templated films deteriorated during the hydro treatment due to a large percentage of silanol groups (Si-OH) which react with water. The hybrid membranes underwent a decrease in the H2/CO2 selectivity of only 1% whereas for the non-templated membrane a 21% decrease was observed. The transport mechanism of the hybrid membranes is activated as permeation increased with temperature. The activation energy for the permeation of H2 is positive while negative for CO2. The H2 permeation obtained was 3x 10 -8 mol.m -2 .s -1 .Pa -1 and permselectivities for H2/CO2 and H2/N2 varied between 1-7 and 31-34, respectively.

Spectral peak resolution and speech recognition in quiet: Normal hearing, hearing impaired and cochlear implant listeners

Spectral peak resolution was investigated in normal hearing (NH), hearing impaired (HI), and cochlear implant (CI) listeners. The task involved discriminating between two rippled noise stimuli in which the frequency positions of the log-spaced peaks and valleys were interchanged. The ripple spacing was varied adaptively from 0.13 to 11.31 ripples/octave, and the minimum ripple spacing at which a reversal in peak and trough positions could be detected was determined as the spectral peak resolution threshold for each listener. Spectral peak resolution was best, on average, in NH listeners, poorest in CI listeners, and intermediate for HI listeners. There was a significant relationship between spectral peak resolution and both vowel and consonant recognition in quiet across the three listener groups. The results indicate that the degree of spectral peak resolution required for accurate vowel and consonant recognition in quiet backgrounds is around 4 ripples/octave, and that spectral peak resolution poorer than around 1–2 ripples/octave may result in highly degraded speech recognition. These results suggest that efforts to improve spectral peak resolution for HI and CI users may lead to improved speech recognition

The resolution of complex spectral patterns by cochlear implant and normal-hearing listeners

The differences in spectral shape resolution abilities among cochlear implant ~CI! listeners, and between CI and normal-hearing ~NH! listeners, when listening with the same number of channels ~12!, was investigated. In addition, the effect of the number of channels on spectral shape resolution was examined. The stimuli were rippled noise signals with various ripple frequency-spacings. An adaptive 4IFC procedure was used to determine the threshold for resolvable ripple spacing, which was the spacing at which an interchange in peak and valley positions could be discriminated. The results showed poorer spectral shape resolution in CI compared to NH listeners ~average thresholds of approximately 3000 and 400 Hz, respectively!, and wide variability among CI listeners ~range of approximately 800 to 8000 Hz!. There was a significant relationship between spectral shape resolution and vowel recognition. The spectral shape resolution thresholds of NH listeners increased as the number of channels increased from 1 to 16, while the CI listeners showed a performance plateau at 4–6 channels, which is consistent with previous results using speech recognition measures. These results indicate that this test may provide a measure of CI performance which is time efficient and non-linguistic, and therefore, if verified, may provide a useful contribution to the prediction of speech perception in adults and children who use CIs.

A method to lower the detection limit for optical beat signals from a frequency-dithered stabilized laser

A narrow absorption feature in an atomic or molecular gas (such as iodine or methane) is used as the frequency reference in many stabilized lasers. As part of the stabilization scheme an optical frequency dither is applied to the laser. In optical heterodyne experiments, this dither is transferred to the RF beat signal, reducing the spectral power density and hence the signal to noise ratio over that in the absence of dither. We removed the dither by mixing the raw beat signal with a dithered local oscillator signal. When the dither waveform is matched to that of the reference laser the output signal from the mixer is rendered dither free. Application of this method to a Winters iodine-stabilized helium-neon laser reduced the bandwidth of the beat signal from 6 MHz to 390 kHz, thereby lowering the detection threshold from 5 pW of laser power to 3 pW. In addition, a simple signal detection model is developed which predicts similar threshold reductions.

Canonical Bose gas simulations with stochastic gauges

A technique to simulate the grand canonical ensembles of interacting Bose gases is presented. Results are generated for many temperatures by averaging over energy-weighted stochastic paths, each corresponding to a solution of coupled Gross-Pitaevskii equations with phase noise. The stochastic gauge method used relies on an off-diagonal coherent-state expansion, thus taking into account all quantum correlations. As an example, the second-order spatial correlation function and momentum distribution for an interacting 1D Bose gas are calculated.

Pair correlations in a finite-temperature 1D Bose gas

We calculate the two-particle local correlation for an interacting 1D Bose gas at finite temperature and classify various physical regimes. We present the exact numerical solution by using the Yang-Yang equations and Hellmann-Feynman theorem and develop analytical approaches. Our results draw prospects for identifying the regimes of coherent output of an atom laser, and of finite-temperature “fermionization” through the measurement of the rates of two-body inelastic processes, such as photoassociation.

Spectral properties of the tandem Jackson network, seen as a quasi-birth-and-death process

Quasi-birth-and-death (QBD) processes with infinite “phase spaces” can exhibit unusual and interesting behavior. One of the simplest examples of such a process is the two-node tandem Jackson network, with the “phase” giving the state of the first queue and the “level” giving the state of the second queue. In this paper, we undertake an extensive analysis of the properties of this QBD. In particular, we investigate the spectral properties of Neuts’s R-matrix and show that the decay rate of the stationary distribution of the “level” process is not always equal to the convergence norm of R. In fact, we show that we can obtain any decay rate from a certain range by controlling only the transition structure at level zero, which is independent of R. We also consider the sequence of tandem queues that is constructed by restricting the waiting room of the first queue to some finite capacity, and then allowing this capacity to increase to infinity. We show that the decay rates for the finite truncations converge to a value, which is not necessarily the decay rate in the infinite waiting room case. Finally, we show that the probability that the process hits level n before level 0 given that it starts in level 1 decays at a rate which is not necessarily the same as the decay rate for the stationary distribution.

Analysis of multiple gas solid reactions

Multiple gas solid reactions involving one solid and N gaseous reactants are investigated in this study by using a matched asymptotic expansion technique. Two cases are particularly studied. In the first case all N chemical reaction rates are faster than the diffusion rate. While in the second case only M (M < N) chemical reaction rates are faster than the diffusion rate and the rates of the remaining (N-M) chemical reactions are comparable to that of diffusion. For these two cases the solid concentration profile behaves like a travelling wave. In the first case the wave front velocity is contributed linearly by all gaseous reactants (additive law) while in the second case this law does not hold.

On the validity of the shrinking core model in noncatalytic gas solid reaction

By using a matched asymptotic expansion technique, the shrinking core model (SCM) used in non-catalytic gas solid reactions with general kinetic expression is rigorously justified in this paper as a special case of the homogeneous model when the reaction rate is much faster than that of diffusion. The time-pendent velocity of the moving reacted-unreacted interface is found to be proportional to the gas flux at that interface for all geometries of solid particles, and the thickness order of the reaction zone and also the degree of chemical reaction at the interface is discussed in this paper.

Satellite protection and drag reduction using a purging gas flow

We have used the DSMC method to determine contamination (impingement of atmospheric molecules) and the aerodynamic forces on a cold satellite when a protective “purge gas” is ejected from a sting protruding ahead of the satellite. Forward ejection of the purge gas provides the greatest protection for a given mass of purge gas and the aerodynamic drag can be significantly reduced, thus compensating for the backward reaction from the forward ejection. If the purge gas is ejected backward from the sting (towards the satellite) the ejection provides thrust and the net retarding force can be reduced to zero. Contamination can be reduced and the mass of purging gas is less than the mass of conventional rocket propellant required to maintain the orbit of an unprotected satellite.

NMR study of the radiation-induced cross-linking of poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether)

The gamma-radiolysis of poly(tetrafluoroethylene-co-perfuoromethyl vinyl ether) (TFE/PMVE) was investigated using solid state F-19 and C-13 NMR spectroscopy. Chain scission products identified in the polymer were saturated chain ends -CF2CF3 (G = 1.0), methyl ether end groups -CF2OCF3 (G = 0.9), acid end groups -CF2COOH (G = 0.5), and a small amount of terminal unsaturation -CF=CF2 (G = 0.2). A mechanism for the formation of these scission products was proposed and the G value for main chain scission, G(S), was determined to be 1.4. Cross-linking of TFE/PMVE was found to proceed via a Y-linking mechanism. The G value for cross-linking, G(X), was determined to be 0.9. A maximum of 0.2 mol % cross-links were formed under the experimental conditions.

An ESR and NMR study of the gamma radiolysis of a bisphenol-A based polycarbonate and a phthalic acid ester

A study of the gamma-radiolysis of the commercial polymers U-polymer, UP (Unitake) and polycarbonate, PC, (Aldrich) has been undertaken using ESR spectroscopy. The G-value of radical formation at 77 K has been found to be 0.31 +/- 0.01 for UP and 0.5 +/- 0.02 for PC. By using thermal annealing and spectral subtraction, the paramagnetic species formed on irradiation has been assigned. The effect of radiation on the chemical structure of UP and PC has been investigated at ambient temperature and at 423 K. The NMR results show that a new phenol type chain end is formed in the polymers on exposure to gamma-radiation. The G-value of formation of the new phenol ends was estimated to be 0.7 for PC (423 K) and 0.4 for UP (300 K). (C) 1998 John Wiley & Sons, Ltd.