Cross-relaxation dynamics on anomalous saturation processes in low pressure supersonic cw HF chemical laser amplifier

It is assumed that both translational and rotational nonequilibrium cross-relaxations play a role simultaneoulsy in low pressure supersonic cw HF chemical laser amplifier. For two-type models of gas flow medium with laminar and turbulent flow diffusion mixing, the expressions of saturated gain spectrum are derived respectively, and the numerical calculations are performed as well. The numerical results show that turbulent flow diffusion mixing model is in the best agreement with the experimental result.

Chemical sputtering of ta-C: Implications for the deposition of carbon nitride

The majority of attempts to synthesize the theoretically predicted superhard phase β-C3N4 have been driven towards the use of techniques which maximize both the carbon sp3 levels and the amount of nitrogen incorporated within the film. However, as yet no attempt has been made to understand the mechanism behind the resultant chemical sputter process and its obvious effect upon film growth. In this work, however, the chemical sputtering process has been investigated through the use of an as-deposited tetrahedrally bonded amorphous carbon film with a high density nitrogen plasma produced using an rf-based electron cyclotron wave resonance source. The results obtained suggested the presence of two distinct ion energy dependent regimes. The first, below 100 eV, involves the chemical sputtering of carbon from the surface, whereas the second at ion energies in excess of 100 eV exhibits a drop in sputter rate associated with the subplantation of nitrogen within the carbon matrix. Furthermore, as the sample temperature is increased there is a concomitant decrease in sputter rate suggesting that the rate is controlled by the adsorption and desorption of additional precursor species rather than the thermal desorption of CN. A simple empirical model has been developed in order to elucidate some of the primary reactions involved in the sputter process. Through the incorporation of various previously determined experimental parameters including electron temperature, ion current density, and nitrogen partial pressure the results indicated that molecular nitrogen physisorbed at the ta-C surface was the dominant precursor involved in the chemical sputter process. However, as the physisorption enthalpy of molecular nitrogen is low this suggests that activation of this molecular species takes place only through ion impact at the surface. The obtained results therefore provide important information for the modeling and growth of high density carbon nitride. © 2001 American Institute of Physics.

Different methods of manufacturing FE-based oxygen carrier particles for reforming via chemical looping, and their effect on performance

Chemical looping combustion (CLC) is a means of combusting carbonaceous fuels, which inherently separates the greenhouse gas carbon dioxide from the remaining combustion products, and has the potential to be used for the production of high-purity hydrogen. Iron-based oxygen carriers for CLC have been subject to considerable work; however, there are issues regarding the lifespan of iron-based oxygen carriers over repeated cycles. In this work, haematite (Fe2O3) was reduced in an N2+CO+CO2 mixture within a fluidised bed at 850°C, and oxidised back to magnetite (Fe3O4) in a H2O+N2 mixture, with the subsequent yield of hydrogen during oxidation being of interest. Subsequent cycles started from Fe3O4 and two transition regimes were studied; Fe3O4↔Fe0.947O and Fe 3O4↔Fe. Particles were produced by mechanical mixing and co-precipitation. In the case of co-precipitated particles, Al was added such that the ratio of Fe:Al by weight was 9:1, and the final pH of the particles during precipitation was investigated for its subsequent effect on reactivity. This paper shows that co-precipitated particles containing additives such as Al may be able to achieve consistently high H2 yields when cycling between Fe3O4 and Fe, and that these yields are a function of the ratio of [CO2] to [CO] during reduction, where thermodynamic arguments suggest that the yield should be independent of this ratio. A striking feature with our materials was that particles made by mechanical mixing performed much better than those made by co-precipitation when cycling between Fe3O4 and Fe0.947O, but much worse than co-precipitated particles when cycling between Fe3O 4 and Fe.

Bronze and iron weapons from Luristan

The 30,000 km2 province of Luristan is situated in western Iran and encompasses the upper valleys of the Zagros Mountains. Even today, local tribesmen inhabit Luristan with their settlement patterns similar to ancient times. Several scientific excavations in the Luristan region have uncovered evidence that this particular region was a major attraction for human settlements from the Paleolithic era onwards. In Ancient Iran, the existence of rich mines together with discoveries made by innovative and inventive artisans spurred the growth of the metalworking culture as an art and a skill among early human communities in Ancient Iran. The art of Luristan can be described as the art of nomadic herdsmen and horsemen with an emphasis on the crafting of small, easily portable objects, among these a number of bronze daggers, swords and other weapons. Throughout its history, Luristan was never an ethnic or political entity because Luristan has been occupied by various tribes and races, throughout its history. Next to Elamites, other tribes who inhabited Luristan were the Hurrians, Lullubians, Kutians, and Kassites. As local tribesmen of Luristan were illiterate, information about their history can only be partially reconstructed from the literature of their southern neighbors: the Elamites and Babylonians. Luristan smiths made weapons for both civilizations. The region was later invaded by Assyrians and finally the Iranians settled the area and absorbed the local tribes. Following an accidental find by the local inhabitants in Luristan in 1928 CE, a number of unlawful diggings reveal a number of metal objects made of bronze and iron that showed a high level of craftsmanship. These objects were offered for sale on the art market with fancy names to hide their origin. The subsequent scientific excavations several decades after the initial discovery provided fascinating information about the culture of Luristan. The metalworking art of Luristan spans a time period from the third millennium BC to the Iron Age. The artifacts from Luristan seem to possess many unique and distinctive qualities, and are especially noteworthy for the apparently endless, intricate diversity and detail that they characteristically depict. The bronze artifacts found in or attributed to Luristan can be each be classed under five separate heads: a) arms and armor, including swords, dirks, daggers, axes, mace heads, spearheads, shields, quiver plaques, protective bronze girdles, helmets; b) implements related to horsemanship, including decorative or ornamental objects for horses as well as bits and snaffles; c) items for personal adornment and hygiene, including anklets, bangles, bracelets, finger rings, earrings and tweezers; d) ceremonial and ritual objects, including talismans, idols, pins, anthropomorphic and zoomorphic figurines; and e) utilitarian objects comprising various vessels and tools, including beakers, bowls and jugs. The scope of this article is limited to a discussion of the bronze and iron weapons made in Luristan. The techniques used for making bronze weapons in Luristan included: casting with open molds, casting with close molds, and casting with lost wax process. For metal sheets used for quiver plaques and bronze protective belts, the hammering technique was used. Edged weapons made in Luristan can be classified into: a) daggers, dirks, and swords with tangs; b) daggers, dirks, and swords with flanges; and c) daggers, dirks, and swords with cast-on hilts. Next to bronze, iron was also used for making weapons such as the characteristic weapon from this area, the iron mask sword.

Effects of Translational Nonequilibrium on Performance of Flowing Chemical Oxygen-Iodine Laser

The effect of the translational nonequilibrium on performance modeling of flowing chemical oxygen-iodine lasers (COIL) is emphasized in this paper. The spectral line broadening (SLB) model is a basic factor for predicting the performances of flowing COIL. The Voigt profile function is a well-known SLB model and is usually utilized. In the case of gas pressure in laser cavity less than 5 torr, a low pressure limit expression of the Voigt profile function is used. These two SLB models imply that ail lasing particles can interact with monochromatic laser radiation. Basically, the inhomogeneous broadening effects are not considered in these two SLB models and they cannot predict the spectral content. The latter requires consideration of finite translational relaxation rate. Unfortunately, it is rather difficult to solve simultaneously the Navier-Stokes (NS) equations and the conservation equations of the number of lasing particles per unit volume and per unit frequency interval. In the operating condition of flowing COIL, it is possible to obtain a perturbational solution of the conservational equations for lasing particles and deduce a new relation between the gain and the optical intensity, i.e., a new gain-saturation relation. By coupling the gain-saturation relation with other governing equations (such as the NS equations, chemical reaction equations and the optical model of gain-equal-loss), We have numerically calculated the performances of flowing COIL. The present results are compared with those obtained by the common rate-equation (RE) model, in which the Voigt profile function and its low pressure limit expression are used. The difference of different model's results is great. For instance, in the case of lasing frequency coinciding with the central frequency of line profile and very low gas pressure, the gain-saturation relation of the present model is quite different with that of the RE model.

Plasma enhanced chemical vapour deposition carbon nanotubes/nanofibres - How uniform do they grow?

The ability to grow carbon nanotubes/nanofibres (CNs) with a high degree of uniformity is desirable in many applications. In this paper, the structural uniformity of CNs produced by plasma enhanced chemical vapour deposition is evaluated for field emission applications. When single isolated CNs were deposited using this technology, the structures exhibited remarkable uniformity in terms of diameter and height (standard deviations were 4.1 and 6.3% respectively of the average diameter and height). The lithographic conditions to achieve a high yield of single CNs are also discussed. Using the height and diameter uniformity statistics, we show that it is indeed possible to accurately predict the average field enhancement factor and the distribution of enhancement factors of the structures, which was confirmed by electrical emission measurements on individual CNs in an array.

Plasma enhanced chemical vapour deposited carbon nanotubes for field emission applications

Plasma Enhanced Chemical Vapour Deposition is an extremely versatile technique for directly growing multiwalled carbon nanotubes onto various substrates. We will demonstrate the deposition of vertically aligned nanotube arrays, sparsely or densely populated nanotube forests, and precisely patterned arrays of nanotubes. The high-aspect ratio nanotubes (∼50 nm in diameter and 5 microns long) produced are metallic in nature and direct contact electrical measurements reveal that each nanotube has a current carrying capacity of 107-108 A/cm2, making them excellent candidates as field emission sources. We examined the field emission characteristics of dense nanotube forests as well as sparse nanotube forests and found that the sparse forests had significantly lower turn-on fields and higher emission currents. This is due to a reduction in the field enhancement of the nanotubes due to electric field shielding from adjacent nanotubes in the dense nanotube arrays. We thus fabricated a uniform array of single nanotubes to attempt to overcome these issues and will present the field emission characteristics of this.

Electrical and field emission investigation of individual carbon nanotubes from plasma enhanced chemical vapour deposition

Plasma enhanced chemical vapour deposition (PECVD) is a controlled technique for the production of vertically aligned multiwall carbon nanotubes for field emission applications. In this paper, we investigate the electrical properties of individual carbon nanotubes which is important for designing field emission devices. PECVD nanotubes exhibit a room temperature resistance of 1-10 kΩ/μm length (resistivity 10-6 to 10-5 Ω m) and have a maximum current carrying capability of 0.2-2 mA (current density 107-108 A/cm2). The field emission characteristics show that the field enhancement of the structures is strongly related to the geometry (height/radius) of the structures and maximum emission currents of ∼ 10 μA were obtained. The failure of nanotubes under field emission is also discussed. © 2002 Elsevier Science B.V. All rights reserved.

Kinetics of the chemical looping oxidation of H2 by a co-precipitated mixture of CuO and Al2O3

Chemical-looping combustion (CLC) has the inherent property of separating CO2 from flue gases. Instead of air, it uses an oxygen-carrier, usually in the form of a metal oxide, to provide oxygen for combustion. When used for the combustion of gaseous fuels, such as natural gas, or synthesis gas from the gasification of coal, the technique gives a stream of CO2 which, on an industrial scale, would be sufficiently pure for geological sequestration. An important issue is the form of the metal oxide, since it must retain its reactivity through many cycles of complete reduction and oxidation. Here, we report on the rates of oxidation of one constituent of synthesis gas, H2, by co-precipitated mixtures of CuO+Al2O3 using a laboratory-scale fluidised bed. To minimise the influence of external mass transfer, and also of errors in the measurement of [H2], particles sized to 355-500μm were used at low [H2], with the temperature ranging from 450 to 900°C. Under such conditions, the reaction was slow enough for meaningful measurements of the intrinsic kinetics to be made. The reaction was found to be first order with respect to H2. Above ∼800°C, the reaction of CuO was fast and conformed to the shrinking core mechanism, proceeding via the intermediate, Cu2O, in: 2CuO+H2→Cu2O+H2O, ΔH1073 K0=- 116.8 kJ/mol; Cu2O+H2→2Cu+H2O, ΔH1073 K0-80.9 kJ/mol. After oxidation of the products Cu and Cu2O back to CuO, the kinetics in subsequent cycles of chemical looping oxidation of H2 could be approximated by those in the first. Interestingly, the carrier was found to react at temperatures as low as 300°C. The influence of the number of cycles of reduction and oxidation is explored. Comparisons are drawn with previous work using reduction by CO. Finally, these results indicate that the kinetics of reaction of the oxygen carrier with gasifier synthesis gases is very much faster than rates of gasification of the original fuel. © 2010 The Institution of Chemical Engineers.

Immunosensor Interface Based on Physical and Chemical Immunogylobulin G Adsorption onto Mixed Self-Assembled Monolayers

An immunosensor interface based on mixed hydrophobic self-assembled monolayers (SAMs) of methyl and carboxylic acid terminated thiols with covalently attached human Immunoglobulin G (hIgG), is investigated. The densely packed and organised SAMs were characterised by contact angle measurements and cyclic voltammetry. The effect of the non-ionic surfactant, Tween 20, in preventing nonspecific adsorption is addressed by ellipsometry during physical and covalent hIgG immobilization on pure and mixed SAMs, respectively. It is clearly demonstrated that nonspecific adsorption due to hydrophobic interactions of hIgG on methyl ended groups is totally inhibited, whereas electrostatic/hydrogen bonding interactions with the exposed carboxylic groups prevail in the presence of surfactant. Results of ellipsometry and Atomic Force Microscopy, reveal that the surface concentration of covalently immobilized hIgG is determined by the ratio of COOH/CH3-terminated thiols in SAM forming solution. Moreover, the ellipsometric data demonstrates that the ratio of bound anti-hIgG/hIgG depends on the density of hIgG on the surface and that the highest ratio is close to three. We also report the selectivity and high sensitivity achieved by chronoamperometry in the detection of adsorbed hIgG and the reaction with its antibody.

Semi-gas kinetics model for performance modeling of flowing chemical oxygen-iodine lasers (COIL)

A semi-gas kinetics (SGK) model for performance analyses of flowing chemical oxygen-iodine laser (COIL) is presented. In this model, the oxygen-iodine reaction gas flow is treated as a continuous medium, and the effect of thermal motions of particles of different laser energy levels on the performances of the COIL is included and the velocity distribution function equations are solved by using the double-parameter perturbational method. For a premixed flow, effects of different chemical reaction systems, different gain saturation models and temperature, pressure, yield of excited oxygen, iodine concentration and frequency-shift on the performances of the COIL are computed, and the calculated output power agrees well with the experimental data. The results indicate that the power extraction of the SGK model considering 21 reactions is close to those when only the reversible pumping reaction is considered, while different gain saturation models and adjustable parameters greatly affect the output power, the optimal threshold gain range, and the length of power extraction.

Gain saturation effects of a flowing chemical oxygen-iodine laser

A new oxygen-iodine medium gain model is developed to include pumping and deactivation of the upper laser levels of the iodine atoms, hyperfine and translation relaxation, as well as the flowing effect. The rate equations for gain of a supersonic flowing cw oxygen-iodine laser (COIL) are described when the medium is stimulated by a single-mode field. The general solution of the self-consistency integral equation is obtained. The result shows that the saturation behaviour in low pressure of the COIL differs from both the inhomogeneous and homogeneous broadening, and exhibits an 'anomalous' saturation phenomenon.