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.

Atomic Latin squares of order eleven

A Latin square is pan-Hamiltonian if the permutation which defines row i relative to row j consists of a single cycle for every i j. A Latin square is atomic if all of its conjugates are pan-Hamiltonian. We give a complete enumeration of atomic squares for order 11, the smallest order for which there are examples distinct from the cyclic group. We find that there are seven main classes, including the three that were previously known. A perfect 1-factorization of a graph is a decomposition of that graph into matchings such that the union of any two matchings is a Hamiltonian cycle. Each pan-Hamiltonian Latin square of order n describes a perfect 1-factorization of Kn,n, and vice versa. Perfect 1-factorizations of Kn,n can be constructed from a perfect 1-factorization of Kn+1. Six of the seven main classes of atomic squares of order 11 can be obtained in this way. For each atomic square of order 11, we find the largest set of Mutually Orthogonal Latin Squares (MOLS) involving that square. We discuss algorithms for counting orthogonal mates, and discover the number of orthogonal mates possessed by the cyclic squares of orders up to 11 and by Parker's famous turn-square. We find that the number of atomic orthogonal mates possessed by a Latin square is not a main class invariant. We also define a new sort of Latin square, called a pairing square, which is mapped to its transpose by an involution acting on the symbols. We show that pairing squares are often orthogonal mates for symmetric Latin squares. Finally, we discover connections between our atomic squares and Franklin's diagonally cyclic self-orthogonal squares, and we correct a theorem of Longyear which uses tactical representations to identify self-orthogonal Latin squares in the same main class as a given Latin square.

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.

Growth of Bose-Einstein condensates from thermal vapor

We report on a quantitative study of the growth process of 87Rb Bose-Einstein condensates. By continuous evaporative cooling we directly control the thermal cloud from which the condensate grows. We compare the experimental data with the results of a theoretical model based on quantum kinetic theory. We find quantitative agreement with theory for the situation of strong cooling, whereas in the weak cooling regime a distinctly different behavior is found in the experiment.

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.

Quantum dynamics of three coupled atomic Bose-Einstein condensates

The simplest model of three coupled Bose-Einstein condensates is investigated using a group theoretical method. The stationary solutions are determined using the SU(3) group under the mean-field approximation. This semiclassical analysis, using system symmetries, shows a transition in the dynamics of the system from self trapping to delocalization at a critical value for the coupling between the condensates. The global dynamics are investigated by examination of the stable points, and our analysis shows that the structure of the stable points depends on the ratio of the condensate coupling to the particle-particle interaction, and undergoes bifurcations as this ratio is varied. This semiclassical model is compared to a full quantum treatment, which also displays a dynamical transition. The quantum case has collapse and revival sequences superimposed on the semiclassical dynamics, reflecting the underlying discreteness of the spectrum. Nonzero circular current states are also demonstrated as one of the higher-dimensional effects displayed in this system.

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.

Stimulated Raman adiabatic passage from an atomic to a molecular Bose-Einstein condensate

The process of stimulated Raman adiabatic passage (STIRAP) provides a possible route for the generation of a coherent molecular Bose-Einstein condensate (BEC) from an atomic BEC. We analyze this process in a three-dimensional mean-field theory, including atom-atom interactions and nonresonant intermediate levels. We find that the process is feasible, but at larger Rabi frequencies than anticipated from a crude single-mode lossless analysis, due to two-photon dephasing caused by the atomic interactions. We then identify optimal strategies in STIRAP allowing one to maintain high conversion efficiencies with smaller Rabi frequencies and under experimentally less demanding conditions.

Algebraic Bethe ansatz method for the exact calculation of energy spectra and form factors: applications to models of Bose-Einstein condensates and metallic nanograins

In this review we demonstrate how the algebraic Bethe ansatz is used for the calculation of the-energy spectra and form factors (operator matrix elements in the basis of Hamiltonian eigenstates) in exactly solvable quantum systems. As examples we apply the theory to several models of current interest in the study of Bose-Einstein condensates, which have been successfully created using ultracold dilute atomic gases. The first model we introduce describes Josephson tunnelling between two coupled Bose-Einstein condensates. It can be used not only for the study of tunnelling between condensates of atomic gases, but for solid state Josephson junctions and coupled Cooper pair boxes. The theory is also applicable to models of atomic-molecular Bose-Einstein condensates, with two examples given and analysed. Additionally, these same two models are relevant to studies in quantum optics; Finally, we discuss the model of Bardeen, Cooper and Schrieffer in this framework, which is appropriate for systems of ultracold fermionic atomic gases, as well as being applicable for the description of superconducting correlations in metallic grains with nanoscale dimensions.; In applying all the above models to. physical situations, the need for an exact analysis of small-scale systems is established due to large quantum fluctuations which render mean-field approaches inaccurate.

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.