New limits on the possible variation of physical constants

Recent detections of high-redshift absorption by both atomic hydrogen and molecular gas in the radio spectra of quasars have provided a powerful tool for measuring possible temporal and spatial variations of physical 'constants' in the Universe. We compare the frequency of high-redshift hydrogen 21-cm absorption with that of associated molecular absorption in two quasars to place new (1 sigma) upper limits on any variation in y = g(p) alpha(2) (where alpha is the fine-structure constant, and g(p) is the proton g-factor) of \Delta y/y\ < 5 x 10(-6) at redshifts z = 0.25 and 0.68. These quasars are separated by a comoving distance of 3000 Mpc (for H-0=75 km s(-1) Mpc(-1) and q(0) = 0). We also derive limits on the time rates of change of \(g) over dot (p)/(g) over dot (p)\ < 1 x 10(-15) yr(-1) and \(alpha) over dot/(a) over dot\ < 5 x 10(-16) yr(-1) between the present epoch and z = 0.68, These limits are more than an order of magnitude smaller than previous results derived from highredshift measurements.

Improved constraints on possible variation of physical constants from HI 21-cm and molecular QSO absorption lines

Quasar (QSO) absorption spectra provide an extremely useful probe of possible cosmological variation in various physical constants. Comparison of H i 21-cm absorption with corresponding molecular (rotational) absorption spectra allows us to constrain variation in , where α is the fine-structure constant and gp is the proton g-factor. We analyse spectra of two QSOs, PKS 1413+135 and TXS 0218+357, and derive values of at absorption redshifts of and 0.6847 by simultaneous fitting of the H i 21-cm and molecular lines. We find and respectively, indicating an insignificantly smaller y in the past. We compare our results with other constraints from the same two QSOs given recently by Drinkwater et al. and Carilli et al., and with our recent optical constraints, which indicated a smaller α at higher redshifts.

Radio frequency plasma-induced hydrogen bonding on kaolinite

The radio frequency (RF) plasma-modified surfaces of kaolinite were investigated by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) and deuteration techniques to determine the nature of RF plasma-induced surface functional groups, the altered sites in the lattice, and interaction mechanism between RF plasma and the surface of the kaolinite. It has been concluded that the RF plasma-induced infrared (IR) vibration absorption bands at 2805, 3010, and 3100 cm(-1) are attributable to the stretching vibration of hydrogen-bonded hydroxyl groups, and the band at 1407 cm(-1) is attributable to the bending vibration of (HO-)Al-O or (HO-)Si-O groupings with hydrogen-bonded hydroxyl groups. Structural alteration occurred on both the surface and subsurface region of the kaolinite during RF plasma treatment. Further structural alteration or adjustment was also observed on well-modified and well-deuterated kaolinite. There are two types of OD bands visible in the DRIFT spectra of this kaolinite, one type which decreased rapidly as a function of time in moist air, and the other which remained unchanged during the measurement. Furthermore, the appearance of broad IR bands at 3500-3100 cm(-1) as a result of deuteration is evidence of structural disturbance by RF plasma treatment lattice deuteration. An RF plasma-induced hydrogen bonding model on the surface of the kaolinite is proposed.

Microstructure of MmM(5)/Mg multi-layer hydrogen storage films prepared by magnetron sputtering

Multi-layer hydrogen storage thin films with Mg and MmNi(3.5)(CoAlMn)(1.5) (here Mm denotes La-rich mischmetal) as alternative layers were prepared by direct current magnetron sputtering. Transmission electron microscopy investigation shows that the microstructure of the MmNi(3.5)(CoAlMn)(1.5) and Mg layers are significantly different although their deposition conditions are the same. The MmNi(3.5)(CoAlMn)(1.5) layer is composed of two regions: one is an amorphous region approximately 4 nm thick at the bottom of the layer and the other is a nanocrystalline region on top of the amorphous region. The Mg layer is also composed of two regions: one is a randomly orientated nanocrystalline region 50 nm thick at the bottom of the layer and the other is a columnar crystallite region on top of the nanocrystalline region. These Mg columnar crystallites have their [001] directions parallel to the growth direction and the average lateral size of these columnar crystallites is about 100 nm. A growth mechanism of the multi-layer thin films is discussed based on the experiment results. Wiley-Liss, Inc.

Comparative study of hydrogen storage in Li- and K-doped carbon materials - theoretically revisited

Hydrogen adsorption in alkali-doped carbon materials is investigated theoretically. Our calculations show that hydrogen molecules can be physically adsorbed on alkali-doped graphite at 0 K but such an adsorption is thermodynamically unfavourable. The binding energy of hydrogen adsorption decreases significantly with the increase in temperature and becomes nearly zero at ambient temperature. We suggest that it may be unlikely to observe any hydrogen uptake in alkali-doped carbon materials at or above ambient temperature in the TGA (thermogravimetric) system, the previously reported hydrogen uptake in alkali-doped carbon materials was caused by either uncyclable chemisorbed hydrogen on the defects of carbon (defects were produced by repeated heat treatment) and/or moisture adsorption. (C) 2004 Elsevier Ltd. All rights reserved.

The role of Ti as a catalyst for the dissociation of hydrogen on a Mg(0001) surface

In this paper, the dissociative chemisorption of hydrogen on both pure and Ti-incorporated Mg(0001) surfaces are studied by ab initio density functional theory (DFT) calculations. The calculated dissociation barrier of hydrogen molecule on a pure Mg(0001) surface (1.05 eV) is in good agreement with comparable theoretical studies. For the Ti-incorporated Mg(0001) surface, the activated barrier decreases to 0.103 eV due to the strong interaction between the molecular orbital of hydrogen and the d metal state of Ti. This could explain the experimentally observed improvement in absorption kinetics of hydrogen when transition metals have been introduced into the magnesium materials.

Hydrogen storage of magnesium-based nanocomposites system

Hydrogen storage in traditional metallic hydrides can deliver about 1.5 to 2.0 wt pct hydrogen but magnesium hydrides can achieve more than 7 wt pct. However, these systems suffer from high temperature release drawback and chemical instability problems. Recently, big improvements of reducing temperature and increasing kinetics of hydrogenation have been made in nanostructured Mg-based composites. This paper aims to provide an overview of the science and engineering of Mg materials and their nanosized composites with nanostructured carbon for hydrogen storage. The needs in research including preparation of the materials, processing and characterisation and basic mechanisms will be explored. The preliminary experimental results indicated a promising future for chemically stable hydrogen storage using carbon nanotubes modified metal hydrides under lower temperatures.

Hydrogen storage properties of MgH2/SWNT composite prepared by ball milling

A systematic investigation was performed on the hydrogen storage properties of mechano-chemically prepared MgH2/Single-walled carbon nanotube (SWNT) composites. It is found that the hydrogen absorption capacity and hydriding kinetics of the composites were dependent on the addition amount of SWNTs as well as milling time. A 5 wt.% addition of SVVNTs is optimum to facilitate the hydrogen absorption and desorption of MgH2. The composite MgH2/5 wt.% SWNTs milled for 10h can absorb 6.7 wt.% hydrogen within about 2 min at 573 K, and desorb 6 wt.% hydrogen in about 5 min at 623 K. Prolonging the milling time over 10 h leads to a serious degradation on hydrogen storage property of the MgH2/SWNT composite, and property/structure investigations suggest that the property degradation comes from the structure destruction of the SWNTs. (c) 2005 Elsevier B.V. All rights reserved.

Mg-based nanocomposites with high capacity and fast kinetics for hydrogen storage

Magnesium and its alloys have shown a great potential in effective hydrogen storage due to their advantages of high volumetric/ gravimetric hydrogen storage capacity and low cost. However, the use of these materials in fuel cells for automotive applications at the present time is limited by high hydrogenation temperature and sluggish sorption kinetics. This paper presents the recent results of design and development of magnesium-based nanocomposites demonstrating the catalytic effects of carbon nanotubes and transition metals on hydrogen adsorption in these materials. The results are promising for the application of magnesium materials for hydrogen storage, with significantly reduced absorption temperatures and enhanced ab/desorption kinetics. High level Density Functional Theory calculations support the analysis of the hydrogenation mechanisms by revealing the detailed atomic and molecular interactions that underpin the catalytic roles of incorporated carbon and titanium, providing clear guidance for further design and development of such materials with better hydrogen storage properties.

Effect of carbon/noncarbon addition on hydrogen storage behaviors of magnesium hydride

Various Mg/carbon and Mg/noncarbon composite systems were prepared by mechanical milling and their hydrogen storage behaviors were investigated. It was found that all the carbon additives exhibited prominent advantage over the noncarbon additives, such as BN nanotubes (BNNTs) or asbestos in improving the hydrogen capacity and dehydriding/hydriding kinetics of Mg. And among the various carbon additives, purified single-walled carbon nanotubes (SWNTs) exhibited the most prominent catalytic effect on the hydrogen storage properties of Mg. The hydrogen capacities of all Mg/C composites at 573 K reached more than 6.2 wt.% within 10 min, about 1.5 wt.% higher than that of pure MgH2 at the identical operation conditions. Under certain operation temperatures, H-absorption/desorption rates of Mg/carbon systems were over one order of magnitude higher than that of pure Mg. Furthermore, the starting temperature of the desorption reaction of MgH2 has been lowered to 60 K by adding SWNTs. On the basis of the hydrogen storage behavior and structure/phase investigations, the possible mechanism involved in the property improvement of Mg upon adding carbon materials was discussed. (c) 2005 Elsevier B.V. All rights reserved.

Catalytic effects of subsurface carbon in the chemisorption of hydrogen on a Mg(0001) surface: an ab-initio study

Ab initio density functional theory (DFT) calculations are performed to explore possible catalytic effects on the dissociative chemisorption of hydrogen on a Mg(0001) surface when carbon is incorporated into Mg materials. The computational results imply that a C atom located initially on a Mg(0001) surface can migrate into the subsurface and occupy an fcc interstitial site, with charge transfer to the C atom from neighboring Mg atoms. The effect of subsurface C on the dissociation of H-2 on the Mg(0001) surface is found to be relatively marginal: a perfect sublayer of interstitial C is calculated to lower the barrier by 0.16 eV compared with that on a pure Mg(0001) surface. Further calculations reveal, however, that sublayer C may have a significant effect in enhancing the diffusion of atomic hydrogen into the sublayers through fcc channels. This contributes new physical understanding toward rationalizing the experimentally observed improvement in absorption kinetics of H2 when graphite or single walled carbon nanotubes (SWCNT) are introduced into the Mg powder during ball milling.

New insights into the interaction of hydrogen atoms with boron-substituted carbon

Boron substitution in carbon materials has been comprehensively investigated using the density functional theory method. It was found that there is a correlation between the stability of the graphene sheet, the distribution of T electrons, the electrostatic potential, and the capability for hydrogen-atom adsorption. Boron substitution destabilizes the graphene structure, increases the density of the electron wave around the substitutional boron atoms, and lowers the electrostatic potential, thus improving the hydrogen adsorption energy on carbon. However, this improvement is only ca. 10-20% instead of a factor of 4 or 5. Our calculations also show that two substitutional boron atoms provide consistent and reliable results, but one substitutional boron results in contradictory conclusions. This is a warning to other computational chemists who work on boron substitution that the conclusion from one substitutional boron might not be reliable.

Ultramicroporous membranes for hydrogen separation

Fuel cell systems offer excellent efficiencies when compared to internal combustion engines, which result in reduced fuel consumption and greenhouse gas emissions. One of the areas requiring research for the success of fuel cell technology is the H2 fuel purification to reduce CO, which is a poison to fuel cells. Molecular sieve silica (MSS) membranes have a potential application in this area. In this work showed activated transport, a characteristic of ultramicroporous (dp

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.