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.

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.

Experimental and theoretical investigations of adsorption hysteresis and criticality in MCM-41: Studies with O-2, Ar, and CO2

MCM-41 materials of six different pore diameters were prepared and characterized using X-ray diffraction, transmission electron microscopy, helium pycnometry, small-angle neutron scattering, and gas adsorption (argon at 77.4 and 87.4 K, nitrogen and oxygen at 77.4 K, and carbon dioxide at 194.6 K). A recent molecular continuum model of the authors, previously used for adsorption of nitrogen at 77.4 K, was applied here for adsorption of argon, oxygen, and carbon dioxide. While model predictions of single-pore adsorption isotherms for argon and oxygen are in satisfactory agreement with experimental data, significant deviation was found for carbon dioxide, most likely due to its high quadrupole moment. Predictions of critical pore diameter, below which reversible condensation occurs: were possible by the model and found to be consistent with experimental estimates, for the adsorption of the various gases. On the other hand, existing models such as the Barrett-Joyner-Halenda (BJH), Saito-Foley, and Dubinin-Astakhov models were found to be inadequate, either predicting an incorrect pore diameter or not correlating the isotherms adequately. The wall structure of MCM-41 appears to be close to that of amorphous silica, as inferred from our skeletal density measurements.

A compact shock-assisted free-piston driver for impulse facilities

A free-piston driver that employs entropy-raising shock processes with diaphragm rupture has been constructed, which promises significant theoretical advantages over isentropic compression. Results from a range of conditions with helium and argon driver gases are reported. Significant performance gains were achieved in some test cases. Heat losses are shown to have a strong effect on driver processes. Measurements compare well with predictions from a quasi-one-dimensional numerical code.

The investigation of optimal bombardment parameters for transient and stable transgene expression in sorghum

This report outlines the development of optimized particle inflow gun (PIG) parameters for producing transgenic sorghum (Sorghum bicolor (L.) Moench). Both transient and stable expression were examined when determining these parameters. The uidA reporter gene (GUS) encoding beta -glucuronidase was used in transient experiments and the green fluorescent protein (GFP) used to monitor stable expression. Initially, optimization was conducted using leaf segments, as the generation of sorghum callus in sufficiently large quantities is time-consuming. Following leaf optimization, experiments were conducted using callus, identifying a high similarity between the two tissue types (r(s) = 0.83). High levels of GUS expression were observed in both leaf and callus material when most distant from the DNA expulsion point, and using a pressure greater than 1800 kPa. A higher level of expression was also observed when the aperture of the helium inlet valve was constricted. Using the optimized conditions (pressure of 2200 kPa, distance to target tissue of 15 cm from the expulsion point, and the aperture of the helium inlet valve at one full turn), three promoters (Ubiquitin, Actin1 and CaMV 35S) were evaluated over a 72-h period using GUS as the reporter gene. A significantly higher number of GUS foci were counted with the Ubiquitin construct over this period, compared to the Actin1 and CaMV 35S constructs. Stable callus sectors (on 2 mg l(-1) bialaphos) with GFP expression were visualized for as long as 6 wk post-bombardment. Using this optimized protocol, several plants were regenerated after having been bombarded with the pAHC20 construct (containing the bar gene), with molecular evidence confirming integration.

Investigation of the flow field of a highly heated jet of air

Measurements of mean and fluctuating velocity and temperature and their self- and cross-products to the third-order are presented for a heated axisymmetric air jet. Froude numbers in the range of 3500 13,190, Reynolds numbers in the range of 3470-8500 and non-dimensional streamwise distances. X*, from 0.27 to 1.98 are covered by the data. It was found that turbulence intensity decreases for the heated jet in the region between the inertia dominated and the buoyancy dominated regions which is contrary to findings with helium jets mixing with ambient air to produce density fluctuations. The effects of heating on the turbulent kinetic energy budget and the temperature variance budget show small differences for the inertia dominated region and the intermediate region which help to explain the transition process to the far field plume region. Constants are evaluated for the isotropic eddy diffusivity and generalised gradient hypothesis models as well as the scalar variance model. No significant effect of heating on the dissipation time-scale ratio was found. A novel wire array with an inclined cold wire was used. Measurements obtained with this probe are found to lead to asymmetries in some of the higher-order products. Further investigation suggested that the asymmetries are attributable to an as yet unreported interference effect produced by the leading prong of the inclined temperature wire, The effect may also have implications for inclined velocity wires which contain a temperature component when used in heated flows. (C) 2002 Elsevier Science Inc. All rights reserved.

Study on diffusion and flow of benzene, n-hexane and CCl4 in activated carbon by a differential permeation method

In this paper the diffusion and flow of carbon tetrachloride, benzene and n-hexane through a commercial activated carbon is studied by a differential permeation method. The range of pressure is covered from very low pressure to a pressure range where significant capillary condensation occurs. Helium as a non-adsorbing gas is used to determine the characteristics of the porous medium. For adsorbing gases and vapors, the motion of adsorbed molecules in small pores gives rise to a sharp increase in permeability at very low pressures. The interplay between a decreasing behavior in permeability due to the saturation of small pores with adsorbed molecules and an increasing behavior due to viscous flow in larger pores with pressure could lead to a minimum in the plot of total permeability versus pressure. This phenomenon is observed for n-hexane at 30degreesC. At relative pressure of 0.1-0.8 where the gaseous viscous flow dominates, the permeability is a linear function of pressure. Since activated carbon has a wide pore size distribution, the mobility mechanism of these adsorbed molecules is different from pore to pore. In very small pores where adsorbate molecules fill the pore the permeability decreases with an increase in pressure, while in intermediate pores the permeability of such transport increases with pressure due to the increasing build-up of layers of adsorbed molecules. For even larger pores, the transport is mostly due to diffusion and flow of free molecules, which gives rise to linear permeability with respect to pressure. (C) 2002 Elsevier Science Ltd. All rights reserved.

Modeling of gas adsorption equilibrium over a wide range of pressure: A thermodynamic approach based on equation of state

A thermodynamic approach based on the Bender equation of state is suggested for the analysis of supercritical gas adsorption on activated carbons at high pressure. The approach accounts for the equality of the chemical potential in the adsorbed phase and that in the corresponding bulk phase and the distribution of elements of the adsorption volume (EAV) over the potential energy for gas-solid interaction. This scheme is extended to subcritical fluid adsorption and takes into account the phase transition in EAV The method is adapted to gravimetric measurements of mass excess adsorption and has been applied to the adsorption of argon, nitrogen, methane, ethane, carbon dioxide, and helium on activated carbon Norit R I in the temperature range from 25 to 70 C. The distribution function of adsorption volume elements over potentials exhibits overlapping peaks and is consistently reproduced for different gases. It was found that the distribution function changes weakly with temperature, which was confirmed by its comparison with the distribution function obtained by the same method using nitrogen adsorption isotherm at 77 K. It was shown that parameters such as pore volume and skeleton density can be determined directly from adsorption measurements, while the conventional approach of helium expansion at room temperature can lead to erroneous results due to the adsorption of helium in small pores of activated carbon. The approach is a convenient tool for analysis and correlation of excess adsorption isotherms over a wide range of pressure and temperature. This approach can be readily extended to the analysis of multicomponent adsorption systems. (C) 2002 Elsevier Science (USA).

Surface diffusion of strongly adsorbing vapors in activated carbon by a differential permeation method

Conventional methods to determine surface diffusion of adsorbed molecules are proven to be inadequate for strongly adsorbing vapors on activated carbon. Knudsen diffusion permeability (B-k) for strongly adsorbing vapors cannot be directly estimated from that of inert gases such as helium. In this paper three models are considered to elucidate the mechanism of surface diffusion in activated carbon. The transport mechanism in all three models is a combination of Knudsen diffusion, viscous flow and surface diffusion. The collision reflection factor f (which is the fraction of molecules undergoing collision to the solid surface over reflection from the surface) of the Knudsen diffusivity is assumed to be a function of loading. It was found to be 1.79 in the limit of zero loading, and decreases as loading increases. The surface diffusion permeability increases sharply at very low pressures and then starts to decrease after it has reached a maximum (B(mum)s) at a threshold pressure. The initial rapid increase in the total permeability is mainly attributed to surface diffusion. Interestingly the B(mum)s for all adsorbates appear at the same volumetric adsorbed phase concentration, suggesting that the volume of adsorbed molecules may play an important role in the surface diffusion mechanism in activated carbon. (C) 2003 Elsevier Ltd. All rights reserved.

High-pressure adsorption of supercritical gases on activated carbons: An improved approach based on the density functional theory and the bender equation of state

Adsorption of nitrogen, argon, methane, and carbon dioxide on activated carbon Norit R1 over a wide range of pressure (up to 50 MPa) at temperatures from 298 to 343 K (supercritical conditions) is analyzed by means of the density functional theory modified by incorporating the Bender equation of state, which describes the bulk phase properties with very high accuracy. It has allowed us to precisely describe the experimental data of carbon dioxide adsorption slightly above and below its critical temperatures. The pore size distribution (PSD) obtained with supercritical gases at ambient temperatures compares reasonably well with the PSD obtained with subcritical nitrogen at 77 K. Our approach does not require the skeletal density of activated carbon from helium adsorption measurements to calculate excess adsorption. Instead, this density is treated as a fitting parameter, and in all cases its values are found to fall into a very narrow range close to 2000 kg/m(3). It was shown that in the case of high-pressure adsorption of supercritical gases the PSD could be reliably obtained for the range of pore width between 0.6 and 3 run. All wider pores can be reliably characterized only in terms of surface area as their corresponding excess local isotherms are the same over a practical range of pressure.

Multipole expansion of strongly focussed laser beams

Multipole expansion of an incident radiation field-that is, representation of the fields as sums of vector spherical wavefunctions-is essential for theoretical light scattering methods such as the T-matrix method and generalised Lorenz-Mie theory (GLMT). In general, it is theoretically straightforward to find a vector spherical wavefunction representation of an arbitrary radiation field. For example, a simple formula results in the useful case of an incident plane wave. Laser beams present some difficulties. These problems are not a result of any deficiency in the basic process of spherical wavefunction expansion, but are due to the fact that laser beams, in their standard representations, are not radiation fields, but only approximations of radiation fields. This results from the standard laser beam representations being solutions to the paraxial scalar wave equation. We present an efficient method for determining the multipole representation of an arbitrary focussed beam. (C) 2003 Elsevier Science Ltd. All rights reserved.

Weathering geochronology by (U-Th)/He dating of goethite

Nine samples of supergene goethite (FeOOH) from Brazil and Australia were selected to rest the suitability of this mineral for (U-Th)/He dating. Measured He ages ranged from 61 to 8 Ma and were reproducible to better than a few percent despite very large Variations in [U] and [Th]. In all Samples with internal stratigraphy or independent age constraints, the He ages corroborated the expected relationship's. These data demonstrate that internally consistent He ages can be obtained on goethite. but do not prove quantitative 4 He retention. To assess possible diffusive He loss, stepped-heating experiments were performed on two goethite samples that were subjected to proton irradiation to produce a homogeneous distribution of spallogenic He-3. The He-3 release pattern indicates the presence of at least two diffusion domains, one with high helium retentivity and the other with very low retentivity at Earth surface conditions. The low retentivity domain, which accounts for similar to 5% of He-3, contains no natural He-4 and may represent poorly crystalline or intergranular material which has lost all radiogenic He-4 by diffusion in nature. Diffusive loss of He-3 from the high retentivity domain is independent of the macroscopic dimensions of the analyzed polycrystalline aggregate, so probably represents diffusion from individual micrometer-size goethite crystals. The He-2/He-3 evolution during the incremental heating experiments shows that the high retentivity domain has retained 90%-95% of its radiogenic helium. This degree of retentivity is in excellent agreement with that independently predicted from the helium diffusion coefficients extrapolated to Earth surface temperature and held for the appropriate duration. Considering both the high and low retentivity domains, these data indicate that one of the samples retained 90% of its radiogenic He-4 over 47.5 Ma and the other retained 86% over 12.3 Ma. Thus while diffusive-loss corrections to supergene goethite He ages are required. these initial results indicate that the corrections are not extremely large and can be rigorously quantified using the proton-irradiation He-4/He-3 method. Copyright (C) 2005 Elsevier Ltd.

Dual-symmetric Lagrangians in quantum electrodynamics: I. Conservation laws and multi-polar coupling

By using a complex field with a symmetric combination of electric and magnetic fields, a first-order covariant Lagrangian for Maxwell's equations is obtained, similar to the Lagrangian for the Dirac equation. This leads to a dual-symmetric quantum electrodynamic theory with an infinite set of local conservation laws. The dual symmetry is shown to correspond to a helical phase, conjugate to the conserved helicity. There is also a scaling symmetry, conjugate to the conserved entanglement. The results include a novel form of the photonic wavefunction, with a well-defined helicity number operator conjugate to the chiral phase, related to the fundamental dual symmetry. Interactions with charged particles can also be included. Transformations from minimal coupling to multi-polar or more general forms of coupling are particularly straightforward using this technique. The dual-symmetric version of quantum electrodynamics derived here has potential applications to nonlinear quantum optics and cavity quantum electrodynamics.

Weathering Geochronology by (U-Th)/He Dating of Geothite

Ten samples of supergene goethite (FeOOH) from Brazil and Australia were selected to test the suitability of this mineral for (U-Th)/He dating. Measured He ages ranged from 8 to 61 Ma, and were reproducible to better than a few percent despite very large variations in [U] and [Th]. In all samples with internal stratigraphy or independent age constraints, the He ages honored the expected relationships. These data demonstrate that internally consistent He ages can be obtained on goethite, but do not prove quantitative 4He retention. To assess possible diffusive He loss, stepped-heating experiments were performed on two goethite samples that were subjected to proton irradiation to produce a homogeneous distribution of spallogenic 3He. The 3He release pattern indicates the presence of at least two diffusion domains, one with high helium retentivity and the other with very low retentivity at Earth surface conditions. The low retentivity domain, which accounts for ~ 5% of 3He, contains no natural 4He, and may represent poorly crystalline or intergranular material which has lost all radiogenic 4He by diffusion in nature. Diffusive loss of 3He from the high retentivity domain is independent of the macroscopic dimensions of the analyzed polycrystalline aggregate, so probably represents diffusion from individual micrometer-size goethite crystals. The 4He/3He evolution during the step heating experiments shows that the high retentivity domain has retained 90-95% of its radiogenic helium. This degree of retentivity is in excellent agreement with that independently predicted from the helium diffusion coefficients extrapolated to Earth surface temperature and held for the appropriate duration. These data indicate that one of the samples retained 90% of its radiogenic 4He over 46.8 Ma and the other retained 86% over 11.9 Ma. Thus while diffusive-loss corrections to supergene goethite He ages are required, these initial results indicate that the corrections are not extremely large and can be rigorously quantified using the proton-irradiation 4He/3He method.

(U-Th)/He and 40Ar/39Ar Geochronology of Weathering, Hamersley Province, Australia: Implications for weathering history and landscape Evolution

(U–Th)/He dating of goethite, when combined with quantification of diffusive 4He loss by the 4He/3He methodology, provides reliable corrected ages for minerals precipitated in weathering profiles. We have combined (U–Th)/He dating of supergene goethite with 40Ar/39Ar dating of supergene manganese oxides to study the weathering history and landscape evolution in the Hamersley Province, northwestern Australia. Incremental heating 40Ar/39Ar analysis of 187 grains of Mn oxides from 65 samples (44 hand specimens) collected from weathering profiles at seven field sites across the Hamersley Province yield precipitation ages ranging from 63.4 ± 0.9 to 1.5 ± 0.2 Ma. These results, combined with previous results of 40Ar/39Ar dating of Mn oxides (Vasconcelos, 1998 Vasconcelos, P.V., 1998. Unpub. report, pp. 1–278.Vasconcelos, 1998 and Cochrane, 2003), reveal a protracted and episodic history of weathering and landscape evolution, which was already ongoing in Late Cretaceous and spans the Palaeogene and Neogene. Seventy-three grains of goethite from 39 samples extracted from 21 hand specimens, collected from the same field sites where the Mn oxides originated, were dated by the (U–Th)/He method. Internally consistent (U–Th)/He ages, which range from 84.3 ± 12.2 to 3.3 ± 0.5 Ma, have been obtained for most samples when corrections are applied for 10% helium diffusive loss. The geochronological results obtained show remarkable similarity in the distribution of ages associated with supergene mineral precipitation. The widespread occurrence of iron oxides such as goethite in soils and weathering profiles and the successful application of (U–Th)/He dating of goethite offers great opportunities for extracting the wealth of palaeoclimatic and palaeoenvironmental information recorded by these profiles on the surface of terrestrial planets such as Earth and Mars.